TWI729973B - Durable anti-reflective articles - Google Patents

Abstract

Embodiments of durable, anti-reflective articles are described. In one or more embodiments, the article includes a substrate and an anti-reflective coating disposed on the major surface. The article exhibits an average light transmittance of about 94% or greater over an optical wavelength regime and/or an average light reflectance of about 2% or less over the optical wavelength regime, as measured from an anti-reflective surface. In some embodiments, the article exhibits a maximum hardness of about 8 GPa or greater as measured by a Berkovich Indenter Hardness Test along an indentation depth of about 50 nm or greater and a b* value, in reflectance, in the range from about -5 to about 1 as measured on the anti-reflective surface only at all incidence illumination angles in the range from about 0 degrees to about 60 degrees under an International Commission on Illumination illuminant.

Description

Durable anti-reflective objects 【Cross-reference related applications】

This application claims the U.S. Provisional Patent Application No. 62/098,836 filed on December 31, 2014, and the U.S. Provisional Patent Application No. 62/098,819 filed on December 31, 2014, and the U.S. Provisional Patent Application No. 62/098,819 filed on December 31, 2014, in accordance with the patent laws and regulations. U.S. Provisional Patent Application No. 62/028,014 filed on July 23, 2014, U.S. Provisional Patent Application No. 62/010,092 filed on June 10, 2014, and U.S. Provisional Patent Filed on May 12, 2014 Application No. 61/991,656 has priority rights. This application relies on the full content of these US provisional patent applications and the full content of these US provisional patent applications is incorporated herein by reference.

The present invention relates to durable anti-reflection objects and methods for making durable anti-reflection objects, and more particularly to objects that have multiple anti-reflection coatings and exhibit abrasion resistance, low reflectance, and colorless penetration and/or reflection.

Cover objects are often used to protect key devices in electronic products, provide a user interface for input and/or display, and/or many other functions. Such products include mobile devices such as smartphones, mp3 players and tablets. Covering objects also include building objects, transportation objects (such as objects used in automotive applications, trains, airplanes, ships, etc.), electrical objects, or any objects that require some transparency, scratch resistance, abrasion resistance, or any combination of the foregoing. These applications often require strong optical performance characteristics such as scratch resistance and maximum light penetration and minimum reflection. In addition, some cover applications require that the color presented or seen during reflection and/or penetration does not change significantly with the viewing angle. In display applications, this is because if the reflected or penetrating color changes greatly with the viewing angle, the product user will see the color or brightness of the display change, which will reduce the display. The viewing quality of the monitor. In other applications, color changes may improperly affect aesthetic requirements or other functional requirements.

The use of various anti-reflective coatings can improve the optical performance of the cover; however, it is known that anti-reflective coatings are easily worn or worn. Abrasion can jeopardize any improvement in optical properties that can be achieved by the anti-reflective coating. For example, optical filters are often made of multi-layer coatings with different refractive indices, and made of optically transparent dielectric materials (such as oxides, nitrides, and fluorides). Most of the typical oxides used in optical filters are materials with wide energy gaps and do not have the mechanical properties, such as hardness, required for mobile devices, building parts, transportation objects, or home appliances. Nitride and diamond-like coatings have high hardness values, but such materials do not have the required penetration rate for the application.

Abrasion damage includes sliding back and forth contact with objects (such as fingers) from the reverse side. In addition, abrasion damage will generate heat, leading to degradation of the chemical bonds of the membrane material, and causing the cover glass to peel off and other types of damage. Since wear damage usually takes longer than a single event that caused a scratch, the configuration coating material will also be oxidized due to wear damage, further reducing the durability of the coating.

Therefore, there is a need for a new cover article and a method for manufacturing the cover article that are wear-resistant and have improved optical performance.

An embodiment of a durable anti-reflective object is described here. In one or more embodiments, the object includes a substrate and an anti-reflective coating, and the anti-reflective coating has a thickness of about 1 micrometer (μm) or less (for example, about 800 nanometers (nm) or less) and is placed on the main surface And form an anti-reflective surface. After 500 cycles of wear, using the Taber test to measure the anti-reflective surface, the article will exhibit wear resistance. In one or more embodiments, when measured with a turbidity meter with an aperture, the object exhibits abrasion resistance (measurement of an anti-reflective surface) including a turbidity of about 1% or less, wherein the diameter of the aperture is about 8 millimeters (mm ). In one or more embodiments, when measured with an atomic force microscope, the object exhibits abrasion resistance (measurement of an anti-reflection surface) including an average roughness Ra of about 12 nm or less. In one or more embodiments, an imaging spherical surface is used for scattering measurement and a 2mm aperture at a wavelength of 600nm is used. When penetration is measured with normal incidence, the object exhibits abrasion resistance (measurement The anti-reflection surface) contains a scattered light intensity of about 0.05 or less (unit: 1/steradian) at a polar scattering angle of about 40 degrees or less. In some examples, when using an imaging sphere for scattering measurement and a 2mm aperture at a wavelength of 600nm, when measuring penetration with normal incidence, the object exhibits abrasion resistance (measurement of anti-reflective surface) including extreme scattering of about 20 degrees or less The intensity of scattered light at the angle is about 0.1 or less (unit: 1/steradian).

One or more object embodiments have excellent optical performance in terms of light penetration and/or light reflection. In one or more embodiments, the average light transmittance (measured on the anti-reflective surface) of the object within a light wavelength range (for example, about 400 nm to about 800 nm or about 450 nm to about 650 nm) is about 94% or more (for example, About 98% or more). In some embodiments, the average light reflectance (measured on the anti-reflective surface) of the object in the light wavelength range is about 2% or less (for example, about 1% or less). The average light transmittance or average light reflectance of the object has an average amplitude of about 1% or less in the light wavelength range. In one example, when using a light source to observe the anti-reflective surface, the role deviation of the object from the reference illumination angle to about 2 degrees to about 60 degrees incident illumination angle is less than about 10 (for example, 5 or less, 4 or less, 3 or less, 2 or less or about 1 or less). Example light sources include any of CIE F2, CIE F10, CIE F11, CIE F12, and CIE D65. In one or more embodiments, under all incident illumination angles of about 0 to about 60 degrees, the object exhibits a b* value of about -5 to about 1 in the CIE L*, a*, b* colorimetric system. From about -5 to about 0 or from about -4 to about 0. Alternatively or in addition, when measuring an anti-reflective surface, some of the object embodiments exhibit a penetration color (or penetration color coordinate) and/or a reflection color (or reflection color coordinate), and the color shift of the reference point deviating from the reference point is less than about approx. 2. In one or more embodiments, the reference point is the origin (0,0) of the L*a*b* color space (or color coordinates (a*=0, b*=0)), coordinates (a*= -2, b*=-2) or the penetration or reflection color coordinates of the substrate. Observe the character cast, reference color cast and color coordinates (a* and/or b*) under a D65 and/or F2 light source.

In one or more embodiments, the anti-reflective coating includes a plurality of layers. For example, in some embodiments, the anti-reflective coating includes a period including a first low RI layer and a second high RI layer. The loop section may include a first low RI layer and a second high RI layer placed on the first low RI layer, or vice versa. In some In the embodiment, the loop section includes the third layer. The anti-reflective coating may include a plurality of cyclic nodes, alternating the first low RI layer and the second high RI layer. The anti-reflective coating may include up to about 10 loops.

In one or more embodiments, at least one of the first low RI layer and the second high RI layer includes an optical thickness (n*d) of about 2 nm to about 200 nm. In some embodiments, the anti-reflective coating includes a plurality of layers and has one or more second high RI layers, so that the combined thickness of the second high RI layer is less than about 500 nm or less.

In some embodiments, the article includes a layer with a refractive index greater than about 1.9. The material used for this layer includes SiN _x , SiO _x N _y , Si _u Al _v O _x N _y , AlN _x , AlO _x N _y or a combination of the above.

In some examples, the article may include additional layers, such as easy-to-clean coatings, diamond-like carbon ("DLC") coatings, scratch-resistant coatings, or combinations of the foregoing. Such coatings can be placed on or between anti-reflective coatings. If a scratch-resistant coating is included, this layer can be placed on the anti-reflective coating to form a scratch-resistant surface. According to the Berkovich indenter hardness test, the hardness of the example scratch-resistant coating is about 8 GPa to about 50 GPa.

In some embodiments, the article includes a layer with a refractive index greater than about 1.9. The material used for this layer includes SiN _x , SiO _x N _y , Si _u Al _v O _x N _y , AlN _x , AlO _x N _y or a combination of the above.

The substrate used in one or more article embodiments may include an amorphous substrate or a crystalline substrate. The amorphous substrate includes glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali alumino borosilicate glass. In some embodiments, the glass is strengthened and includes a compressive stress (CS) layer with a surface CS of at least 250 MPa, the CS layer extending from the chemically strengthened glass surface to a depth of layer (DOL) of at least about 10 μm within the strengthened glass.

The additional features and advantages of the present invention will be described in detail later. Those who are familiar with this technology will become better to some extent after referring to or implementing the described embodiments, including the following detailed description of the embodiments, the scope of patent application and the drawings. Clear and easy to understand.

It should be understood that the above summary description and the following detailed description are only examples, and it is intended to provide an overview or structure to understand the nature and characteristics of the scope of the patent application. The attached drawings provide further understanding, Therefore, it should be incorporated into and form part of the specification. The drawings depict one or more embodiments, and together with the description of the embodiments are used to explain the principles and operations of the different embodiments.

100‧‧‧Object

110‧‧‧Substrate

112, 114, 116, 118‧‧‧surface

120‧‧‧Anti-reflective coating

120A-C‧‧‧Floor

122‧‧‧Anti-reflective surface

130‧‧‧Circulation Festival

130A‧‧‧Low RI layer

130B‧‧‧High RI layer

130C‧‧‧Floor

131‧‧‧Cover

140‧‧‧Coating

200‧‧‧Substrate

210, 220, 230, 340, 250, 260, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 505, 510, 515, 520, 530, 540, 550, 560, 570, 580, 590, 600, 605, 610, 615, 620, 625, 630, 635, 640, 650, 660, 670, 680, 690‧‧‧Floor

Figure 1 is a side view of an object according to one or more embodiments; Figure 2 is a side view of an object according to one or more specific embodiments; Figure 3 is a side view of an object according to one or more embodiments; Figure 4 is a side view of an object according to one or more embodiments; Figure 5 is a side view of an object according to one or more embodiments; Figure 6 is a side view of an object according to one or more embodiments; Figure 7 The side view of the object according to Example 1; Figure 8 is the reflectivity curve of the object according to Example 1, Figure 9 is the simulated reflectivity curve of the object according to Example 2, and Figure 10 is the reflectivity curve of the object according to Example 3. Simulated reflectivity graph; Figure 11 is a simulated reflectivity graph of the object according to Example 3, with an additional DLC coating; Figure 12 is a schematic diagram of the object according to Example 4; Figure 13 is a list of the object of Example 4 Side reflectance spectrum, this figure shows the reflectance when the incident illumination angle is 0 degrees to about 60 degrees; Figure 14 is the reflectance color spectrum of the object in Example 4, this figure shows the use of a 10-degree observer, the different viewing angles The reflection color under the light source; Figure 15 is a schematic diagram of the object according to Example 5; Figure 16 is the one-sided reflectance spectrum of the object of Example 5, which shows the reflectivity when the incident illumination angle is from 0 degrees to about 45 degrees; Figure 17 is the reflection color spectrum of the object of Example 5. This figure shows the reflection color of the D65 light source with different viewing angles using a 10-degree observer; Figure 18 is a schematic diagram of the object according to Example 6; Figure 19 is an example The single-sided reflectance spectrum of the object of 6, the figure shows the reflectance when the incident illumination angle is 0 degrees to about 60 degrees; the 20th figure is the reflectance color spectrum of the object of example 6, the figure shows the use of a 10-degree observer, in The reflection colors under different light sources at different viewing angles; Figure 21 is a schematic diagram of the object according to Example 7; Figure 22 is the single-sided reflection spectrum of the object of Example 7, which shows the incident illumination angle from 0 degrees to about 60 degrees Figure 23 is the reflection color spectrum of the object in Example 7. This figure shows the reflection color under different light sources with different viewing angles using a 10-degree observer; Figure 24 is a schematic diagram of the object according to Example 8; Figure 25 is the single-sided reflectance spectrum of the object of Example 8, which shows the reflectance when the incident illumination angle is from 0 degrees to about 60 degrees; Figure 26 is the reflectance color spectrum of the object of Example 8, which shows the use of 10 degrees. Observer, reflected colors under different light sources with different viewing angles; Figure 27 is the single-sided reflectance spectrum of the object of Model Example 9, which shows the reflectivity when the incident illumination angle is from 0 degrees to about 60 degrees; Figure 28 The figure shows the reflection color spectrum of the object in Example 9, which shows the reflection color under different light sources with different viewing angles using a 10-degree observer; Figure 29 shows the single-sided reflection spectrum of the object in Model Example 10A, which shows The reflectivity when the incident illumination angle is from 0 degrees to about 60 degrees; Figure 30 is the single-sided reflectance spectrum of the object of model example 10B, which shows the reflectance when the incident illumination angle is from 0 degrees to about 60 degrees; Figure 31 is the reflectance color spectrum of the object of example 10A, which shows the use of The reflected color of the 10-degree observer under different light sources at different viewing angles; Figure 32 is the reflected color spectrum of the object in Example 10B, which shows the reflected color under different light sources with different viewing angles using the 10-degree observer Figure 33 shows the scattered light intensity values of Examples 12, 13 and Comparative Examples 15, 16, 17 after and without the Taber test; Figure 34 shows Examples 12, 13 and Comparative Example 14, 17.18 AFM roughness statistical graphs measured after the Taber test; Figure 35 shows the single-sided reflectance spectrum of the object of Example 19, which shows the reflectance when the incident illumination angle is from 0 degrees to about 60 degrees; Section 36 The figure shows the reflection and transmission color spectrum of the object in Example 19, which shows the reflection and transmission colors under different light sources with different viewing angles using a 10-degree observer; Figure 37 shows the measured transmission color coordinates of Example 21 And reflection color coordinates; Figure 38 is the reflectance spectrum of Example 21 under different illumination angles; Figure 39 is the two-surface penetration and reflection spectra of Example 21; Figure 40 is the hardness measurement with indentation depth and coating Graph of thickness change.

Different embodiments will now be described in detail, and examples of the embodiments are shown in the accompanying drawings.

1, according to one or more embodiments, the object 100 includes a substrate 110 and an anti-reflective coating 120 placed on the substrate. The substrate 110 includes opposite major surfaces 112 and 114 and opposite minor surfaces 116 and 118. Figure 1 shows that the anti-reflective coating 120 is placed on the first opposite major surface 112; On the first opposite major surface 112, the anti-reflective coating 120 may be placed on the second opposite major surface 114 and/or one or two opposite minor surfaces. The anti-reflective coating 120 forms an anti-reflective surface 122.

The anti-reflective coating 120 includes at least one layer with at least one material. The term "layer" can include a single layer or include one or more sublayers. The sub-layers can be in direct contact with each other. The sub-layers can be composed of the same material or two or more different materials. In one or more alternative embodiments, the sub-layers have interposers of different materials interposed therebetween. In one or more embodiments, the layer may include one or more continuous and uninterrupted layers and/or one or more discontinuous and discontinuous layers (ie, layers with different materials formed adjacent to each other). The layers or sublayers can be formed by any method known in the art, including discrete deposition or continuous deposition processes. In one or more embodiments, only a continuous deposition process or a discrete deposition process may be used to form the layer.

The term "distribution" as used herein includes coating, depositing and/or forming materials onto a surface using any method known in the art. The configuration material may constitute the layer. The term "placed on" includes the case where the material is formed to the surface so that the material directly contacts the surface, and includes the case where the material is formed on the surface and one or more intervening layers are located between the disposition material and the surface. The intermediary material may constitute the layer.

The anti-reflective layer 120 of one or more embodiments can be said to have abrasion resistance measured by different methods after at least about 500 cycles of wear according to the Taber test. This field is familiar with various types of abrasion testing, such as ASTM D1044-99, the use of the test method provided by Taber's abrasion media. Using different types of wear media, abrasive geometry and operation, pressure, etc., can produce ASTM D1044-99-related modified wear methods, providing reproducible measurement of wear or wear trajectory, in order to distinguish the wear resistance of different samples. For example, different test conditions are usually suitable for soft plastic versus hard inorganic test samples. The described embodiment has been tested by Taber. This is a specific modified version of ASTM D1044-99 to clearly and reproduce the durability of different samples. The samples mainly contain hard inorganic materials, such as oxide glass and oxide or nitride coatings. . The term "Taber Test" as used here refers to the use of the Taber linear grindstone 5750 (TLA 5750) and the accessories supplied by Taber Company in an environment with a temperature of about 22°C±3°C and a relative humidity of up to about 70%. testing method. TLA 5750 includes CS-17 grinding stone material, the diameter of the grinding stone is 6.7mm. Etabl tested wear samples, especially using turbidity Degree and bidirectional penetration distribution function (CCBTDF) measurement and evaluation of wear damage. In the Taber test, the procedure for abrading each sample includes placing the TLA 5750 and the flat sample support on a rigid surface, and fixing the TLA 5750 and the sample support to the surface. Before the Etabl test abraded each sample, the grindstone was regrinded with the new S-14 smooth tape adhered to the glass. The grinding stone undergoes 10 regrind cycles, the cycle speed is 25 cycles/min, the stroke length is 1 inch, and no additional weight is added (that is, the total weight used during the regrind is about 350 grams. This system combines the mandrel and clamping The weight of the collet of the grindstone). The procedure then includes operating TLA 5750 to wear the sample, where the sample is placed on the sample support, the support contacts the grind stone and supports the weight applied to the grind stone, the cycle speed is 25 cycles/min, the stroke length is 1 inch, and the application is The total weight of the pre-sample is 850 grams (that is, except for the combined weight of the mandrel and collet of 350 grams, an auxiliary weight of 500 grams is applied). The procedure includes forming two wear tracks on each sample for reproducibility, and each wear track on each sample wears each sample, counting 500 cycles.

In one or more embodiments, the anti-reflective coating 120 of the wear article 100 is tested by Etabl, the wear side is measured with the Haze-Gard plus® turbidimeter supplied by BYK Gardner, and the aperture is used on the source port. With a diameter of 8mm, the object will show a turbidity of about 10% or less. With or without any additional coating (including the additional coating 140, which will be described later), the article 100 of one or more embodiments exhibits this wear resistance. In some embodiments, the haze may be about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or Or less, about 2% or less, about 1% or less, about 0.5% or less, or about 0.3% or less. In some specific embodiments, the turbidity of the article 100 is from about 0.1% to about 10%, from about 0.1% to about 9%, from about 0.1% to about 8%, from about 0.1% to about 7%, from about 0.1% to about 6%, about 0.1% to about 5%, about 0.1% to about 4%, about 0.1% to about 3%, about 0.1% to about 2%, about 0.1% to about 1%, 0.3% to about 10%, About 0.5% to about 10%, about 1% to about 10%, about 2% to about 10%, about 3% to about 10%, about 4% to about 10%, about 5% to about 10%, about 6 % To about 10%, about 7% to about 10%, about 1% to about 8%, about 2% to about 6%, about 3% to about 5%, and all ranges and subranges in between.

An alternative method of quantifying abrasion resistance is also included here. In one or more embodiments, when an atomic force microscope (AFM) is used to measure the surface profile, for example, an 80×80 micron area or multiple 80×80 micron areas of the anti-reflection coating 120 (to sample more wear areas) are measured, The object 100 on which the anti-reflective coating 120 is worn by the Taber test also exhibits abrasion resistance. Surface roughness statistics such as RMS roughness, Ra roughness, and peak-to-valley surface height can be evaluated from AFM surface scans. In one or more embodiments, the average surface roughness (Ra) of the article 100 (or more specifically the anti-reflective coating 120) after being abraded by the above-mentioned Taber test is about 50 nm or less, about 25 nm or less, About 12 nm or less, about 10 nm or less, or about 5 nm or less.

In one or more embodiments, according to light scattering measurement, the object 100 exhibits abrasion resistance after being worn by the Taber test. In one or more embodiments, the light scattering measurement includes a bidirectional reflectance distribution function (BRDF) or bidirectional transmission distribution function (BTDF) measurement ^{using a Radiant Zemax IS-SA™ instrument.} This instrument can flexibly measure light scattering at any input angle from normal to about 85 degrees incident reflection and normal to about 85 degrees incident penetration. It can also capture all reflected or penetrating scattered light output into 2π spherical degrees (reflective or Transmission full hemisphere). In one embodiment, according to the normal incidence of BTDF to measure and analyze the penetrating scattered light in a selected angle range, such as a polar angle of about 10 degrees to about 80 degrees and any angle range within, the object 100 exhibits abrasion resistance. It can analyze and calculate the integral of the omni-directional angle range, or select a specific azimuth angle limit, such as about 0 degrees to 90 degrees azimuth angle. In the case of linear wear, the azimuth direction that is substantially perpendicular to the wear direction is expected to improve the signal-to-noise ratio of the light scattering measurement. In one or more embodiments, when the Radiant Zemax IS-SA tool is used in CCBTDF mode with normal incidence penetration and a monochromator with a 2mm aperture and a wavelength set to 600nm is used to measure the anti-reflective coating 120, and approximately When evaluating the extreme scattering angle from 15 degrees to about 60 degrees (for example, about 20 degrees or about 40 degrees in particular), the scattered light intensity of the object 100 is less than about 0.1, about 0.05 or less, about 0.03 or less, about 0.02 Or less, about 0.01 or less, about 0.005 or less, or about 0.003 or less (unit is 1/steradian). The normal incidence penetration is reported to be zero-degree penetration, which can be represented by the instrument software as 180-degree incidence. In one or more embodiments, the scattered light intensity can be measured along the azimuth direction, which is substantially perpendicular to the wear direction of the Taber test wear sample. In one example, the Taber test can take about 10 cycles to about 1000 cycles and all values in between. These light intensity values can also correspond to input light intensity of less than about 1%, less than about 0.5%, less than about 0.2%, or less than about 0.1%, and the polar scattering angle is scattered to be greater than about 5 degrees, greater than about 10 degrees, and greater than about 30. Degrees or greater than about 45 degrees.

Generally speaking, the BTDF test with normal incidence is closely related to the penetration turbidity measurement, because both measure the amount of light scattered through the sample (or in this case, the object 100 after the anti-reflective coating 120 is worn) . Compared with turbidity measurement, BTDF measurement provides better sensitivity and more detailed angle information. BTDF can change the scattering measurement into different polar angles and azimuth angles. For example, let people selectively evaluate the scattering azimuth angle. In the linear Taber test, the scattering azimuth angle is substantially perpendicular to the wear direction (these are the angles at which light is most scattered from linear wear). The penetration turbidity is essentially the integration of all scattered light measured from the normal incident BTDF to the entire polar angle (greater than about ±2.5 degrees) hemisphere.

The anti-reflective coating 120 and the object 100 can be described in terms of the hardness measured by the Berkovich indenter hardness test. The "Berkovich indenter hardness test" used here involves imprinting the surface with a diamond Berkovich indenter to measure the hardness of the surface material. The Berkovich indenter hardness test includes embossing the anti-reflective surface 122 or the surface of the anti-reflective coating 120 (or the surface of any one or more layers of the anti-reflective coating) of the object with a diamond Berkovich indenter to form an indentation of about 50 nm Indentation depth to about 1000nm (or the entire thickness of the anti-reflective coating or layer, whichever is thinner), and measurement along the entire indentation depth range or indentation depth section (for example, about 100nm to about 600nm) The maximum hardness of the indentation, this is usually used "Oliver, WC, Pharr, GM, "An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments", J.Mater.Res .,Vol.7,No .6,1992,1564-1583" and "Oliver,WC,Pharr,GM,"Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology", J.Mater.Res .,Vol.19, No. 1, 2004, 3-20" method. The "hardness" used here refers to the maximum hardness, not the average hardness.

Generally, in nanoindentation measurement methods (such as using a Berkovich indenter) and the coating is harder than the underlying substrate, the measured hardness initially seems to increase due to the formation of a plastic zone at a shallow indentation depth, and then at a deeper indentation depth Increase to the maximum or horizontal top. Subsequently, at deeper indentation depths, the hardness begins to decrease due to the influence of the underlying substrate. Using a substrate with a greater hardness than the coating has the same effect; however, at deeper indentation depths, the hardness increases due to the influence of the underlying substrate.

The indentation depth range and the hardness value in certain indentation depth ranges can be selected to identify the specific hardness response of the optical film structure and layer without being affected by the underlying substrate. When measuring the hardness of the optical film structure (placed on the substrate) with the Berkovich indenter, the permanent deformation zone (plastic zone) of the material is related to the hardness of the material. When imprinting, the elastic stress field far exceeds the permanent deformation zone. As the indentation depth increases, the apparent hardness and modulus are affected by the interaction of the stress field with the underlying substrate. The influence of the substrate on the hardness occurs at a deeper indentation depth (that is, usually at a depth greater than about 10% of the optical film structure or layer thickness). Furthermore, it is more complicated that the hardness response requires a certain minimum load to form complete plasticity during the imprinting process. Before a certain minimum load, the hardness tends to increase roughly.

At a small indentation depth (which can also be characterized as a small load) (for example, up to about 50 nm), the apparent hardness of the material appears to increase substantially relative to the indentation depth. The small indentation depth range does not represent the true hardness measurement, but reflects the formation of the above-mentioned plastic zone, which is related to the limited radius of curvature of the indenter. At the middle indentation depth, the apparent hardness is close to the maximum. At deeper indentation depths, as the indentation depth increases, the influence of the substrate gradually increases. Once the indentation depth exceeds 30% of the optical film structure thickness or layer thickness, the hardness begins to decrease sharply.

Figure 40 shows how the measured hardness varies with the depth of the indentation and the thickness of the coating. As shown in Figure 40, the hardness measured at the middle and deeper indentation depths (where the hardness is close to and maintained at the maximum value) depends on the material or layer thickness. Figure 40 shows the hardness response of four different AlO _x N _{y layers with different thicknesses.} The hardness of each layer was measured using the Berkovich indenter hardness test. The 500nm thick layer has the maximum hardness at the indentation depth of about 100nm to about 180nm, and then the hardness drops sharply at the indentation depth of about 180nm to about 200nm, which means that the substrate hardness affects the hardness measurement. The 1000 nm thick layer has a maximum hardness at an indentation depth of about 100 nm to about 300 nm, and then the hardness decreases sharply at an indentation depth greater than about 300 nm. The 1500nm thick layer has the maximum hardness at an indentation depth of about 100nm to about 550nm, and the 2000nm thick layer has the maximum hardness at an indentation depth of about 100nm to about 600nm. Although FIG. 40 illustrates a thick single layer, the same behavior can be observed in thin coatings and those that include multiple layers, such as the anti-reflective coating 120 of the described embodiment.

In some embodiments, when the anti-reflective surface 122 is measured by the Berkovich indenter hardness test, the hardness of the anti-reflective coating 120 is greater than about 5 GPa. The hardness of the anti-reflective coating 120 may be about 8 GPa or more, about 10 GPa or more, or about 12 GPa or more. When the anti-reflective surface 122 is measured by the Berkovich indenter hardness test, the hardness of the object 100 including the anti-reflective coating 120 and any additional coatings may be about 5 GPa or more, about 8 GPa or more, or about 10 GPa. Pa or more or about 12 GPa or more. Anti-reflective coating 120 and/or object 100 along about 50nm or more or about 100nm or more (e.g., about 100nm to about 300nm, about 100nm to about 400nm, about 100nm to about 500mm, about 100nm to about 600nm, about 200nm to An indentation depth of about 300 nm, about 200 nm to about 400 nm, about 200 nm to about 500 nm, or about 200 nm to about 600 nm) can have this measured hardness value.

According to the Berkovich indenter hardness test measurement, the anti-reflective coating 120 may have at least one layer, and the hardness of the layer (the surface of the measurement layer, such as the surface of the second high RI layer 130B in Figure 2) is about 12 GPa or more, about 13 GPa or more, about 14 GPa or more, about 15 GPa or more, about 16 GPa or more, about 17 GPa or more, about 18 GPa or more, about 19 GPa or more, about 20 GPa Pa or more, about 22 GPa or more, about 23 GPa or more, about 24 GPa or more, about 25 GPa or more, about 26 GPa or more, or about 27 GPa or more (up to about 50 GPa Pa). According to the Berkovich indenter hardness test, the hardness of this layer can be about 18 GPa to about 21 GPa. At least one layer is along about 50nm or more or 100nm or more (e.g., about 100nm to about 300nm, about 100nm to about 400nm, about 100nm to about 500nm, about 100nm to about 600nm, about 200nm to about 300nm, about 200nm to about 400nm, The indentation depth of about 200nm to about 500nm or about 200nm to about 600nm can have this measured hardness value. In one or more embodiments, the hardness of the object is greater than the hardness of the substrate (measure the opposite surface of the anti-reflective surface).

In one or more embodiments, when a Berkovich indenter is used to imprint the surface to measure the anti-reflective surface 122, the elastic modulus of the anti-reflective coating 120 or individual layers of the anti-reflective coating may be about 75 GPa or more , About 80 GPa or more or about 85 GPa or more. These modulus values may represent the modulus measured very close to the anti-reflective surface 122, such as an indentation depth of 0-50 nm, or may represent the modulus measured at a deeper indentation depth, such as about 50-1000 nm.

The light interference between the reflected waves from the anti-reflective coating 120/air interface and the anti-reflective coating 120/substrate 110 interface will cause the spectral reflectance and/or transmittance to fluctuate, which in turn produces obvious colors on the object 100. The term "transmittance" as used herein is defined as the percentage of incident light power in a specific wavelength range that penetrates a material (such as an object, a substrate, or an optical film or part). The term "reflectivity" is also defined as the percentage of incident light power within a specific wavelength range that is reflected from a material (such as an object, substrate, or optical film or part). Transmittance and reflectance are measured using specific line widths. In one or more embodiments, the spectral resolution of the transmission and reflection characteristics is less than 5 nm or 0.02 electron volts (eV). The reflected color is more obvious. Because the spectral reflectance fluctuates with the incident illumination angle, the reflection role shifts with the viewing angle. The penetrating role also deviates with the viewing angle due to the fluctuation of the spectral transmittance and the deviation of the incident illumination angle. Seeing the color and the role deviation with the incident illumination angle is usually distracting or offensive to the user of the device, especially under the illumination of bright spectral characteristics, such as fluorescent lamps and some LED lighting. Penetrating character deviation is also a factor of reflecting character deviation, and vice versa. The factors of the penetration and/or reflection of the role deviation also include material absorption (slightly independent of angle), which causes the viewing angle or color to deviate from certain white points defined by the specific light source or the test system, resulting in the role deviation.

The fluctuation can be described in terms of amplitude. The term "amplitude" as used here includes reflection or penetration peak-to-valley changes. The term "average amplitude" includes the average reflection or penetration peak-to-valley variation in the wavelength range of light. The "light wavelength range" used herein includes about 400 nm to about 800 nm, more specifically, about 450 nm to about 650 nm.

Embodiments of the present invention include anti-reflective coatings to provide improved optical performance in terms of being colorless under different light sources and/or having a small role deviation when viewed at different incident illumination angles deviating from normal incidence.

One aspect of the present invention relates to an object. Even when viewed under a light source at different incident angles, the object still exhibits colorless reflection and/or penetration. In one or more embodiments, the object exhibits a reflection and/or penetration deviation of about 5 or less or about 2 or less between the reference illumination angle and any incident illumination angle in the range. The term "color shift" (angle or reference point) used here refers to the change in reflection and/or penetration of the a* and b* of the CIE L*, a*, b* colorimetric system. It should be understood that unless otherwise specified, the L* coordinate of the object is the same at any angle or reference point and does not affect the color cast. For example, the role bias can be determined by the following formula (1): (1)√((a* ₂ -a* ₁ ) ² +(b* ₂ -b* ₁ ) ² ) where a* ₁ and b* _{1 are} used for reference The a* and b* coordinates of the object viewed at the illumination angle (including normal incidence), a* ₂ and b* ₂ represent the a* and b* coordinates of the object viewed at the incident illumination angle, provided that the incident illumination angle is different from the reference illumination angle , In some cases, the difference reference illumination angle is at least about 1 degree, 2 degrees, or about 5 degrees. In some examples, under the light source, when viewed at different incident illumination angles that deviate from the reference illumination angle, the reflection and/or penetration of the object is approximately 10 or less (for example, 5 or less, 4 or less, 3 or less) Or 2 or less). In some examples, the reflection and/or penetration role deviation is about 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less , 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less or 0.1 or less. In some embodiments, the role bias is about zero. The light source can include standard light sources determined by CIE, including A light source (representing tungsten filament lamp), B light source (daylight simulation lighting), C light source (daylight simulation lighting), D series light source (representing natural lighting) and F series light source (representing different Type of fluorescent lamp). In a specific example, under the CIE F2, F10, F11, F12, or D65 light source, or more specifically, under the CIE F2 light source, when viewed at an incident illumination angle that deviates from the reference illumination angle, the reflection and/or penetration of the object The transmissive part is about 2 or less.

The reference illumination angle can include normal incidence (i.e. 0 degrees), or deviation from normal incidence 5 degrees, deviation from normal incidence 10 degrees, deviation from normal incidence 15 degrees, deviation from normal incidence 20 degrees, deviation from normal incidence 25 degrees, 30 degrees off normal incidence, 35 degrees off normal incidence, 40 degrees off normal incidence, 50 degrees off normal incidence Degree, 55 degrees off normal incidence, or 60 degrees off normal incidence, assuming that the reference illumination angle differs from the incident illumination angle by at least about 1, 2, or about 5 degrees. The incident illumination angle is relative to the reference illumination angle and deviates from the normal incidence by about 5 degrees to about 80 degrees, about 5 degrees to about 80 degrees, about 5 degrees to about 70 degrees, about 5 degrees to about 65 degrees, and about 5 degrees to about 60 degrees. Degrees, about 5 degrees to about 55 degrees, about 5 degrees to about 50 degrees, about 5 degrees to about 45 degrees, about 5 degrees to about 40 degrees, about 5 degrees to about 35 degrees, about 5 degrees to about 30 degrees, About 5 degrees to about 25 degrees, about 5 degrees to about 20 degrees, about 5 degrees to about 15 degrees, and all ranges and subranges in between. When the reference illumination angle is normal incidence, the object can exhibit the reflection and/or penetration role deviation at and along all incident illumination angles from about 2 degrees to about 80 degrees. In some embodiments, when the incident illumination angle differs from the reference illumination angle by at least about 1, 2, or about 5 degrees, the object can exhibit the reflection at and along all incident illumination angles from about 2 degrees to about 80 degrees. And/or penetrating the character deviation. In one example, the object exhibits 2 or less at any incident illumination angle of about 2 degrees to about 60 degrees, about 5 degrees to about 60 degrees, or about 10 degrees to about 60 degrees deviating from the reference illumination angle (equal to normal incidence) The reflection and/or penetration of the character deviation. In other examples, when the reference illumination angle is 10 degrees and the incident illumination angle is any angle that deviates from the reference illumination angle by about 12 degrees to about 60 degrees, about 15 degrees to about 60 degrees, or about 20 degrees to about 60 degrees, the object Shows a reflection and/or penetration character deviation of 2 or less.

In some embodiments, the role deviation of all angles between the reference illumination angle (for example, normal incidence) and the incident illumination angle of about 20 degrees to about 80 degrees is measured. In other words, it can measure about 0 degrees to 20 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 60 degrees, or about 0 degrees to about 80 degrees. The role deviation of all angles, and the role deviation is less than about 5 or less than about 2.

In one or more embodiments, the object exhibits reflection and/or penetration colors in the CIE L*, a*, b* colorimetric system, so that the light source (including the standard light source determined by CIE, including the A light source (representing tungsten) Light source), B light source (daylight simulation lighting), C light source (daylight simulation lighting), D series light source (representing natural lighting), and F series light source (representing different types of fluorescent lamps), penetrating color or reflecting coordinates The distance from the reference point or the color shift of the reference point is less than about 5 or less than about 2. In a specific example, under the CIE F2, F10, F11, F12 or D65 light source, or more specifically under the CIE F2 light source, to deviate from the reference illumination angle When viewed from the incident illumination angle, the reflected and/or penetrating role of the object is approximately 2 or less. In other words, when measuring the anti-reflective surface 122 whose reference point deviated from the reference point has a color shift of less than about 2, the object exhibits a transmission color (or a transmission color coordinate) and/or a reflection color (or a reflection color coordinate). Unless otherwise specified, the penetrating color or penetrating color coordinate system measures two surfaces of the object, including the anti-reflection surface 122 and the relatively bare surface (ie 114) of the object. Unless otherwise specified, the reflection color or the reflection color coordinates only measure the anti-reflection surface 122 of the object.

In one or more embodiments, the reference point is the origin of the CIE L*, a*, b* colorimetric system (0,0) (or color coordinates (a*=0, b*=0)), color Coordinates (-2, -2) or the penetration or reflection color coordinates of the substrate. It should be understood that unless otherwise specified, the L* coordinate of the object is the same as the reference point and does not affect the color cast. The reference point color shift of the object is defined relative to the substrate, the penetration color coordinate system of the object is compared with the penetration color coordinate of the substrate, and the reflected color coordinate system of the object is compared with the reflection color coordinate of the substrate.

In one or more specific embodiments, the reference point color shift of the transmission color and/or the reflection color is less than 1 or even less than 0.5. In one or more specific embodiments, the reference point color shift of the transmission color and/or the reflection color may be 1.8, 1.6, 1.4, 1.2, 0.8, 0.6, 0.4, 0.2, 0 and all ranges and subranges therebetween. If the reference point is the color coordinate (a*=0, b*=0), the color shift of the reference point can be calculated by the following formula (2).

(2) Reference point color shift=√(( a * _object ) ² +( b * _object ) ² ) If the reference point is the color coordinate (a*=-2, b*=-2), then the following formula (3 ) Calculate the color shift of the reference point.

(3) Reference point color shift=√(( a * _object +2) ² +( b * _object +2) ² ) If the reference point is the color coordinate of the substrate, the color shift of the reference point can be calculated by the following formula (4).

(4) Reference point color shift = √(( a * _object - a * _substrate ) ² + ( b * _object - b * _substrate ) ² )

In some embodiments, when the reference point is any one of the color coordinates of the substrate, the color coordinates (a*=0, b*=0), and the color coordinates (a*=-2, b*=-2), The object presents the penetration color (or penetration color coordinate) and the reflection color (or reflection color coordinate) so that the color shift of the reference point is less than 2.

In one or more embodiments, at all incident illumination angles of about 0 degrees to about 60 degrees (or about 0 degrees to about 40 degrees or about 0 degrees to about 30 degrees), the object has a CIE L* in terms of reflection. , a*, b* colorimetric system presents a b* value (only measuring anti-reflective surface) of about -5 to about 1, about -5 to about 0, about -4 to about 1, or about -4 to about 0.

In one or more embodiments, at all incident illumination angles from about 0 degrees to about 60 degrees (or from about 0 degrees to about 40 degrees or from about 0 degrees to about 30 degrees), the object is in CIE L in terms of penetration. *, a*, b* The b* value presented by the colorimetric system (measures the relative bare surface of the anti-reflective surface and the object) is about -2 to about 2, about -1 to about 2, about -0.5 to about 2, about 0 to about 2, about 0 to about 1, about -2 to about 0.5, about -2 to about 1, about -1 to about 1, or about 0 to about 0.5.

In some embodiments, under D65, A, and F2 light sources, the a* value (anti-reflective surface and relatively bare surface) of the object in terms of penetration is about 0° to about 60° at an incident illumination angle of about 0° to about 60°. -1.5 to about 1.5 (e.g., -1.5 to -1.2, -1.5 to -1, -1.2 to 1.2, -1 to 1, -1 to 0.5, or -1 to 0). In some embodiments, under D65, A, and F2 light sources, the object exhibits a b* value (anti-reflective surface and relatively bare surface) in terms of penetration at an incident illumination angle of about 0 degrees to about 60 degrees. -1.5 to about 1.5 (e.g., -1.5 to -1.2, -1.5 to -1, -1.2 to 1.2, -1 to 1, -1 to 0.5, or -1 to 0).

In some embodiments, under the D65, A, and F2 light sources, the a* value of the object in terms of reflection (anti-reflection surface only) is about -5 to about 5 at an incident illumination angle of about 0 degrees to about 60 degrees. 2 (e.g. -4.5 to 1.5, -3 to 0, -2.5 to 0.25). In some embodiments, under the D65, A, and F2 light sources, the object exhibits a b* value (anti-reflection surface only) of about -7 to about -7 to about 60 degrees at an incident illumination angle of about 0 degrees to about 60 degrees. -1.5.

The object of one or more embodiments or the anti-reflective surface 122 of one or more objects has an average light transmittance of about 95% or more (e.g., about 95.5% or more, about 96%) in the light wavelength range of about 400nm to about 800nm. % Or more, about 96.5% or more, about 97% or more, about 97.5% or more, about 98% or more, about 98.5% or more, or about 99% or more). In some embodiments, the anti-reflective surface 122 of the object or one or more objects has an average light reflectance of about 2% or less (e.g., about 1.5% or less, about 1% or less) in the light wavelength range of about 400 nm to about 800 nm. Or less, about 0.75% or less, about 0.5% or less or About 0.25% or less). The light penetration and light reflection values can be observed in the entire light wavelength range or a selected range of the light wavelength range (for example, the 100nm wavelength range, 150nm wavelength range, 200nm wavelength range, 250nm wavelength range, 280nm wavelength range or 300nm wavelength range of the light wavelength range) . In some embodiments, the light reflection and penetration values are total reflection or total penetration (considering reflection or penetration on the anti-reflection surface 122 and the opposite main surface 114). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (but it can also be measured at an incident illumination angle of 45 degrees or 60 degrees).

且與眼睛的光譜響應有關：

In some embodiments, the object of one or more embodiments or the anti-reflective surface 122 of one or more objects has an average visible light reflectance in the light wavelength range of about 1% or less, about 0.7% or less, about 0.5% or less or about 0.45% or less. The light reflectance value can be exhibited at an incident illumination angle of about 0 degrees to about 20 degrees, about 0 degrees to about 40 degrees, or about 0 degrees to about 60 degrees. The "Optical Reflectance" used here simulates the response of the human eye by weighting the reflectance versus wavelength spectrum based on the sensitivity of the human eye. According to known specifications, such as the CIE color space specification, the light reflectance can also be defined as the brightness or the tristimulus Y value of the reflected light. In formula (5), the average light reflectance is defined as the spectral reflectance R(λ) multiplied by the light source spectrum I(λ) and the color matching function of CIE

And it is related to the spectral response of the eye:

In a specific embodiment, the average visible light reflectance of the anti-reflective surface 122 of one or more objects (that is, when the anti-reflective surface 122 is measured through only one-sided measurement) is about 2% or less, 1.8% or less , 1.5% or less, 1.2% or less, 1% or less, 0.9% or less, 0.7% or less, about 0.5% or less, about 0.45% or less, about 0.4% or less or about 0.35% or less. In some cases, although having a maximum reflection color shift of less than about 5.0, less than about 4.0, less than about 3.0, less than about 2.0, less than about 1.5, or less than about 1.25 at the same time, using D65 illumination, the entire incident illumination angle range ( (About 5 degrees to about 60 degrees) (reference irradiation angle is the normal incidence) of the average visible light reflectance range. The maximum reflected color shift value represents the maximum color point value measured at any angle from about 5 degrees to about 60 degrees from the normal incidence minus the minimum color point value measured at any angle in the same range. This value represents the maximum change in a * (a * -a * _{maximum and minimum),} the maximum change in the maximum change (b * -b * _{maximum minimum)} value b *, or the maximum amount of change in a * and b * values of (√((a* _max-a * _min )2+(b* _max- b* _min ) ² ).

In one or more embodiments, when the anti-reflective surface is measured only at or approximately normal incidence (for example, about 0 to about 10 degrees or about 0 to about 6 degrees), the object will exhibit a reflection spectrum, which has the following characteristics Features: The maximum reflectance and minimum reflectance in the wavelength range of about 400nm to about 480nm (the maximum reflectance in this range is called R400-max, and the minimum reflectance in this range is called R400-min). The maximum reflectance and minimum reflectance in the wavelength range of 500nm to about 600nm (the maximum reflectance in this range is called R500-max, and the minimum reflectance in this range is called R500-min) and between about 640nm and about 710nm The maximum reflectance and minimum reflectance in the wavelength range (the maximum reflectance in the wavelength range of about 640 nm to about 710 nm is called R640-max, and the minimum reflectance in the wavelength range of about 640 nm to about 710 nm is called R640-min). In some embodiments, the reflection spectrum has any one or more of the following: R400-max is greater than R500-max, R400-max is greater than R640-max, R400-min is less than R500-min, and R600-min is less than R500-min. In some embodiments, the reflection spectrum has any one or more of the following: R400-max is about 0.6% to about 1.5%, R400-min is about 0% to about 0.3%, and R500-max is about 0.5% to about 0.9 %, R500-min is about 0.3% to about 0.7%, R640-max is about 0.5% to about 0.9%, and R640-min is about 0 to about 0.3%.

Substrate

The substrate 110 may include an inorganic material, and may include an amorphous substrate, a crystalline substrate, or the foregoing composition. The substrate 110 may be made of man-made materials and/or natural materials (for example, quartz and/or polymers). For example, in some examples, the substrate 110 is characterized by organic, more specifically, polymer. Examples of suitable polymers include, but are not limited to: thermoplastics, including polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), and Esters (including copolymers and blends, including polyethylene terephthalate and polyethylene terephthalate copolymers), polyolefins (PO) and cyclic polyolefins (cyclic PO), polyvinyl chloride (PVC), acrylic polymers, including polymethyl methacrylate (PMMA) (including copolymers and blends), thermoplastic urethane Ester (TPU), polyether imine (PEI) and these polymers are blended with each other. Other example polymers include epoxy, styrenic, phenolic, tripolyamine, and silicone resins.

In some specific embodiments, the substrate 110 specifically excludes polymer, plastic, and/or metal substrates. The substrate is characterized by an alkali-containing substrate (that is, the substrate includes one or more alkali metals). In one or more embodiments, the refractive index of the substrate is about 1.45 to about 1.55. In a specific embodiment, using the ball-to-ring test and using at least 5, at least 10, at least 15, or at least 20 samples to measure, the average surface strain failure of one or more of the substrate 110 relative to the main surface is 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more or Even 2% or more. In certain embodiments, the average surface strain failure of one or more relative major surfaces of the substrate 110 is about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.2%, about 2.4%, about 2.6%, About 2.8% or about 3% or more.

The suitable substrate 110 has an elastic modulus (or Young's modulus) of about 30 GPa to about 120 GPa. In some examples, the elastic modulus of the substrate is about 30 GPa to about 110 GPa, about 30 GPa to about 100 GPa, about 30 GPa to about 90 GPa, about 30 GPa to about 80 GPa , About 30 GPa to about 70 GPa, about 40 GPa to about 120 GPa, about 50 GPa to about 120 GPa, about 60 GPa to about 120 GPa, about 70 GPa to about 120 GPa And all ranges and sub-ranges in between.

In one or more embodiments, the amorphous substrate includes strengthened or non-strengthened glass. Examples of suitable glasses include soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminum borosilicate glass. In some variations, the glass does not contain lithium oxide. In one or more alternative embodiments, the substrate 110 includes a crystalline substrate, such as a glass ceramic substrate (which may be strengthened or unstrengthened), or a single crystal structure, such as sapphire. In one or more specific embodiments, the substrate 110 includes an amorphous base (such as glass) and a crystalline coating (such as a sapphire layer, a polycrystalline aluminum oxide layer, and/or a spinel (MgAl ₂ O ₄ ) layer).

The substrate 110 may be substantially flat or sheet-shaped, but other embodiments may use a curved or other shape or shape of the substrate. The substrate 110 may be substantially light-transmissive, transparent and without light scattering. In this embodiment, the average light transmittance of the substrate in the light wavelength range is about 85% or more, about 86% or more, about 87% or more, about 88% or more, about 89% or more, about 90%. % Or more, about 91% or more, or about 92% or more. In one or more alternative embodiments, the substrate 110 is opaque, or the average light transmittance in the light wavelength range is less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6 %, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0%. In some embodiments, the light reflection and penetration values are total reflection or total penetration (considering reflection or penetration on the two main surfaces of the substrate), or for observing one side of the substrate (that is, only the anti-reflection surface 122, regardless of Relative surface). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (but it can also be measured at an incident illumination angle of 45 degrees or 60 degrees). The substrate 110 can selectively present colors, such as white, black, red, blue, green, yellow, orange, etc.

Additionally or alternatively, based on aesthetics and/or functionality, the physical thickness of the substrate 110 may vary along one or more dimensions. For example, the edge of the substrate 110 may be thicker than the central area of the substrate 110. The length, width, and physical thickness of the substrate 110 can also be changed according to the application or purpose of the object 100.

The substrate 110 can be provided by various processes. For example, when the substrate 110 includes an amorphous substrate, such as glass, various forming methods include a floating glass process and a down-draw process, such as fusion drawing and slot drawing.

Once formed, the substrate 110 can be strengthened into a strengthened substrate. The term "reinforced substrate" as used herein refers to a chemically strengthened substrate, for example, through ion exchange between larger ions and smaller ions on the surface of the substrate. However, other strengthening methods known in the art can also be used to form the strengthened substrate, such as thermal tempering, or the use of mismatched thermal expansion coefficients of various parts of the substrate to generate the compressive stress and central tension zone.

When the substrate is chemically strengthened by an ion exchange process, the ions on the surface of the substrate will be replaced or exchanged with larger ions with the same valence or oxidation state. The ion exchange process is usually carried out by immersing the substrate Into the molten salt bath, the molten salt bath contains larger ions to exchange with the smaller ions of the substrate. Those who are familiar with this technology should understand the parameters of the ion exchange process, including bath composition, temperature, immersion time, the number of times the substrate is immersed in one or more salt baths, the use of multiple salt baths, and additional steps such as annealing and washing, but not The limit generally depends on the composition of the substrate and the predetermined compressive stress (CS), and the layer depth (or layer depth) of the substrate compressive stress caused by the strengthening operation. For example, by immersing in at least one molten salt bath containing salts, such as nitrates, sulfates, and chlorides of larger alkali metal ions, but not limited to this, the alkali metal-containing glass can be made Substrate ion exchange. The temperature of the molten salt bath is generally from about 380°C to about 450°C, and the immersion time is from about 15 minutes to about 40 hours. However, temperatures and immersion times other than those described above can also be used.

In addition, an example of a non-limiting ion exchange process is described in US Patent Application No. 12/500,650 filed by Douglas C. Allan et al. on July 10, 2009, titled "Glass with Compressive Surface for Consumer Applications", in which glass The substrate is immersed in multiple ion exchange baths and there are washing and/or annealing steps between the immersion. This application also claims the priority of US Provisional Patent Application No. 61/079,995 filed on July 11, 2008, in which the glass substrate It is strengthened by immersing in salt baths of different concentrations to undergo multiple continuous ion exchange treatments; and on November 20, 2012, awarded to Christopher M, Lee et al., the United States named "Dual Stage Ion Exchange for Chemical Strengthening of Glass" Patent No. 8,312,739, which also claims priority to U.S. Provisional Patent Application No. 61/084,398 filed on July 29, 2008, in which the glass substrate is ion-exchanged in the first bath diluted with effluent ions , Then immerse in a second bath with a lower ion concentration than the first bath for strengthening. The entire contents of U.S. Patent Application No. 12/500,650 and U.S. Patent No. 8,312,739 are incorporated herein by reference.

The degree of chemical strengthening achieved by ion exchange can be quantified based on parameters such as central tension (CT), surface CS, and depth of layer (DOL). The surface CS is measured near the surface or at different depths in the strengthened glass. The maximum CS value may include the CS (CS _s ) measured on the surface of the strengthened substrate. CT is calculated on the internal area adjacent to the compressive stress layer in the glass substrate, and can be calculated from CS, physical thickness t, and DOL. CS and DOL can be measured by means known in this field. Such methods include the use of commercially available instruments such as FSM-6000 manufactured by Luceo Co., Ltd. (Tokyo, Japan) to measure surface stress (FSM), but not limited to this. The method for measuring CS and DOL is described in the name "Standard Specification for Chemically Strengthened Flat Glass" ASTM 1422C-99 and the name "Standard Test Method for Non-Destructive Photoelastic Measurement of Edge and Surface Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat Glass" ASTM 1279.19779, the full text of the above is based on The way of citation is incorporated into this article. The surface stress measurement is based on the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass substrate. SOC can be measured by known methods in this field, such as optical fiber and four-point bending method, both of which are described in ASTM standard C770-98 (2008) named "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the full text of the above Incorporated into this article by reference, and the block cylinder method. The relationship between CS and CT can be expressed by the formula (1): CT=(CS‧DOL)/( t -2DOL) (1), where t is the physical thickness of the glass object (μm). In each section of the present invention, the unit of CT and CS is megapascals (MPa), the unit of physical thickness t is micrometers (μm) or millimeters (mm), and the unit of DOL is micrometers (μm).

In one embodiment, the surface CS of the reinforced substrate 110 is 250 MPa or more, 300 MPa or more, such as 400 MPa or more, 450 MPa or more, 500 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, or 800 MPa or more. The reinforced substrate may have a DOL of 10 μm or more, 15 μm or more, 20 μm or more (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or more) and/or 10 MPa or more, 20 MPa or more, 30 MPa Pa or more, 40 MPa or more (e.g. 42 MPa, 45 MPa or 50 MPa or more), but less than 100 MPa (e.g. 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or below) CT. In one or more specific embodiments, the reinforced substrate has one or more of the following: surface CS is greater than 500 MPa, DOL is greater than 15 μm, and CT is greater than 18 MPa.

66莫耳%，Na₂O

9莫耳%。在一實施例中，玻璃組成包括至少6重量%的氧化鋁。在進一步實施例中，基板包括具一或更多鹼土氧化物的玻璃組成，使得鹼土氧化物的含量為至少5重量%。在一些實施例中，適合玻璃組成進一步包含K₂O、MgO和CaO的至少一者。在一特定實施例中，用於基板的玻璃組成包含61-75莫耳%的SiO₂；7-15莫耳%的Al₂O₃；0-12莫耳%的B₂O₃；9-21莫耳%的Na₂O；0-4莫耳%的K₂O；0-7莫耳%的MgO；及0-3莫耳%的CaO。 Example glasses that can be used for the substrate include alkali aluminum silicate glass composition or alkali aluminum borosilicate glass composition, although other glass compositions are also included. This type of glass composition can be chemically strengthened by an ion exchange process. An example glass composition includes SiO ₂ , B ₂ O ₃ and Na ₂ O, where (SiO ₂ +B ₂ O ₃₎

66 mol%, Na ₂ O

9 mol%. In one embodiment, the glass composition includes at least 6 wt% alumina. In a further embodiment, the substrate includes a glass composition with one or more alkaline earth oxides such that the content of the alkaline earth oxide is at least 5% by weight. In some embodiments, the suitable glass composition further includes _{at least one of K 2} O, MgO, and CaO. In a specific embodiment, the glass composition used for the substrate includes 61-75 mol% of SiO ₂ ; 7-15 mol% of Al ₂ O ₃ ; 0-12 mol% of B ₂ O ₃ ; 9- 21 mol% Na ₂ O; 0-4 mol% K ₂ O; 0-7 mol% MgO; and 0-3 mol% CaO.

(Li₂O+Na₂O+K₂O)

20莫耳%，0莫耳%

(MgO+CaO)

10莫耳%。 Another example glass composition suitable for a substrate includes: 60-70 mol% SiO ₂ ; 6-14 mol% Al ₂ O ₃ ; 0-15 mol% B ₂ O ₃ ; 0-15 mol% Li ₂ O; 0-20 mol% Na ₂ O; 0-10 mol% K ₂ O; 0-8 mol% MgO; 0-10 mol% CaO; 0-5 mol% % ZrO ₂ ; 0-1 mol% SnO ₂ ; 0-1 mol% CeO ₂ ; less than 50 ppm As ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; of which 12 mol%

(Li ₂ O+Na ₂ O+K ₂ O)

20 mol%, 0 mol%

(MgO+CaO)

10 mol%.

(Li₂O+Na₂O+K₂O)

18莫耳%，2莫耳%

(MgO+CaO)

7莫耳%。 Another example glass composition suitable for a substrate includes: 63.5-66.5 mol% SiO ₂ ; 8-12 mol% Al ₂ O ₃ ; 0-3 mol% B ₂ O ₃ ; 0-5 mol% Li ₂ O; 8-18 mol% Na ₂ O; 0-5 mol% K ₂ O; 1-7 mol% MgO; 0-2.5 mol% CaO; 0-3 mol% % ZrO ₂ ; 0.05-0.25 mol% SnO ₂ ; 0.05-0.5 mol% CeO ₂ ; less than 50 ppm As ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; of which 14 mol%

(Li ₂ O+Na ₂ O+K ₂ O)

18 mol%, 2 mol%

(MgO+CaO)

7 mol%.

In a specific embodiment, the alkali aluminosilicate glass composition suitable for the substrate includes alumina, at least one alkali metal, in some embodiments more than 50 mol% SiO ₂ , and in other embodiments at least 58 Mol% of SiO ₂ , and in some other embodiments, at least 60 mol% of SiO _{2 is included} , wherein _{the ratio of (Al 2} O ₃ +B ₂ O ₃ )/Σ modifier (ie modifier and) It is greater than 1, where the component in the ratio is expressed in mole %, and the modifier is an alkali metal oxide. In a specific embodiment, the glass composition includes: 58-72 mol% of SiO ₂ ; 9-17 mol% of Al ₂ O ₃ ; 2-12 mol% of B ₂ O ₃ ; 8-16 mol% % Na ₂ O; and 0-4 mol% K ₂ O, where _{the ratio of (Al 2} O ₃ +B ₂ O ₃ )/Σ modifier (ie modifier sum) is greater than 1.

SiO₂+B₂O₃+CaO

69莫耳%；Na₂O+K₂O+B₂O₃₊MgO+CaO+SrO>10莫耳%；5莫耳%

MgO+CaO+SrO

8莫耳%；(Na₂O+B₂O₃)-Al₂O₃

2莫耳%；2莫耳%

Na₂O-Al₂O₃

6莫耳%；及4莫耳%

(Na₂O+K₂O)-Al₂O₃

10莫耳%。 In still another embodiment, the substrate includes alkali aluminosilicate glass composition, including: 64-68 mol% of SiO ₂ ; 12-16 mol% of Na ₂ O; 8-12 mol% of Al ₂ O ₃ ; 0-3 mole% of B ₂ O ₃ ; 2-5 mole% of K ₂ O; 4-6 mole% of MgO; and 0-5 mole% of CaO, of which: 66 mole%

SiO ₂ +B ₂ O ₃ +CaO

69 mol%; Na ₂ O+K ₂ O+B ₂ O ₃₊ MgO+CaO+SrO>10 mol%; 5 mol%

MgO+CaO+SrO

8mol%; (Na ₂ O+B ₂ O ₃ )-Al ₂ O ₃

2 mol%; 2 mol%

Na ₂ O-Al ₂ O ₃

6 mol%; and 4 mol%

(Na ₂ O+K ₂ O)-Al ₂ O ₃

10 mol%.

In an alternative embodiment, the substrate includes alkali aluminosilicate glass composition, including: 2 mol% or more Al ₂ O ₃ and/or ZrO ₂ , or 4 mol% or more Al ₂ O ₃ and/ Or ZrO ₂ .

If the substrate 110 includes a crystalline substrate, the substrate may include a single crystal, and the single crystal may include Al ₂ O ₃ . This single crystal substrate is called sapphire. Other materials suitable for crystalline substrates include polycrystalline aluminum oxide layer and/or spinel (MgAl ₂ O ₄ ).

Depending on the situation, the crystalline substrate 110 may include a strengthened or non-strengthened glass ceramic substrate. Examples of suitable glass ceramics include Li ₂ O-Al ₂ O ₃ -SiO ₂ system (i.e. LAS system) glass ceramics, MgO-Al ₂ O ₃ -SiO ₂ system (i.e. MAS system) glass ceramics and/or include main crystal phases Glass ceramics including β-quartz solid solution, β-spodumene, β-cordierite and lithium disilicate. The glass ceramic substrate can be strengthened by the chemical strengthening process. In one or more embodiments, the MAS system glass ceramic substrate can be _{strengthened in Li 2} SO ₄ molten salt to exchange 2Li ⁺ and Mg ²⁺ .

According to one or more embodiments, the physical thickness of the substrate 110 is about 100 μm to about 5 mm. The physical thickness of the example substrate 110 is about 100 μm to about 500 μm (e.g., 100, 200, 300, 400, or 500 μm). The physical thickness of another example substrate 110 is about 500 μm to about 1000 μm (for example, 500, 600, 700, 800, 900, or 1000 μm). The physical thickness of the substrate 110 may be greater than about 1 mm (e.g., about 2, 3, 4 or 5mm). In one or more specific embodiments, the physical thickness of the substrate 110 is 2 mm or less or less than 1 mm. The substrate 110 may be subjected to acid polishing or other treatments to eliminate or reduce the effect of surface cracks.

Anti-reflective coating

As shown in Figure 1, the anti-reflective coating 120 includes a plurality of layers 120A, 120B, and 120C. In some embodiments, one or more layers are placed on the opposite side (ie, major surface 114) of the anti-reflective coating 120 of the substrate 110 (not shown).

The physical thickness of the anti-reflective coating 120 may be about 0.1 μm to about 1 μm. In some examples, the physical thickness of the anti-reflective coating 120 may be about 0.01 μm to about 0.9 μm, about 0.01 μm to about 0.8 μm, about 0.01 μm to about 0.7 μm, about 0.01 μm to about 0.6 μm, about 0.01 μm. To about 0.5 μm, about 0.01 μm to about 0.4 μm, about 0.01 μm to about 0.3 μm, about 0.01 μm to about 0.2 μm, about 0.01 μm to about 0.1 μm, about 0.02 μm to about 1 μm, about 0.03 μm to about 1 μm , About 0.04 μm to about 1 μm, about 0.05 μm to about 1 μm, about 0.06 μm to about 1 μm, about 0.07 μm to about 1 μm, about 0.08 μm to about 1 μm, about 0.09 μm to about 1 μm, about 0.2 μm to about 1 μm, About 0.3 μm to about 1 μm, about 0.4 μm to about 1 μm, about 0.5 μm to about 1 μm, about 0.6 μm to about 1 μm, about 0.7 μm to about 1 μm, about 0.8 μm to about 1 μm, or about 0.9 μm to about 1 μm and in between All ranges and sub-ranges.

In one or more embodiments, the anti-reflective coating 120 includes a loop 130 including two or more layers. In one or more embodiments, two or more layers are characterized by having different refractive indexes from each other. In an embodiment, the recurring section 130 includes a first low RI layer 130A and a second high RI layer 130B. The refractive index of the first low RI layer and the second high RI layer may differ by about 0.01 or more, 0.05 or more, 0.1 or more, or even 0.2 or more.

As shown in FIG. 2, the anti-reflective coating 120 includes a plurality of loop sections 130. A single loop section includes a first low RI layer 130A and a second high RI layer 130B, so when a plurality of loop sections are provided, the first low RI layer 130A (marked with "L" for description) and the second high RI layer 130B (marked with "L") For "H" description) can alternate according to the following layer sequence: L/H/L/H or H/L/H/L, so that the first low RI layer and the second high RI layer along the physical thickness of the anti-reflective coating 120 appear alternately. In the example of Figure 2, the anti-reflective coating 120 includes three loops. In some real In an embodiment, the anti-reflective coating 120 includes at most 25 loops. For example, the anti-reflective coating 120 may include about 2 to about 20 loops, about 2 to about 15 loops, about 2 to about 10 loops, about 2 to about 12 loops, about 3 to about 8. Circulation knots, about 3 to about 6 cyclic knots.

In the embodiment shown in FIG. 2, the anti-reflective coating 120 includes an additional cover layer 131, which may include a material with a lower refractive index than the second high RI layer 130B.

In some embodiments, as shown in Figure 3, the loop section 130 includes one or more third layers 130C. The third layer 130C may have low RI, high RI, or medium RI. In some embodiments, the RI of the third layer 130C is the same as the first low RI layer 130A or the second high RI layer 130B. In some embodiments, the third layer 130C has a medium RI between the RI of the first low RI layer 130A and the RI of the second high RI layer 130B. Alternatively, the refractive index of the third layer 130C may be greater than that of the second high RI layer 130B. The third layer can be provided on the anti-reflective coating 120 according to the following example structures: L _{third layer} /H/L/H/L; H _{third layer} /L/H/L/H; L/H/L/H/ L _{third layer} ; H/L/H/L/H _{third layer} ; L _{third layer} /H/L/H/L/H _{third layer} ; H _{third layer} /L/H/L/H/L _{The third layer} ; L _{third layer} /L/H/L/H; H _{third layer} /H/L/H/L; H/L/H/L/L _{third layer} ; L/H/L/H /H _{third layer} ; L _{third layer} /L/H/L/H/H _{third layer} ; H _{third layer} //H/L/H/L/L _{third layer} ; L/M _{third layer} / H/L/M/H; H/M/L/H/M/L; M/L/H/L/M; and other combinations. In these structures, the "L" without any subscript refers to the first low RI layer, and the "H" without any subscript refers to the second high RI layer. "L _{third sublayer} " refers to the third layer with low RI, "H _{third sublayer} " refers to the third layer with high RI, and "M" refers to the third layer with medium RI. All of the above are relative The first and second floors.

As used herein, "low RI", "high RI" and "medium RI" refer to RI values relative to each other (for example, low RI<medium RI<high RI). In one or more embodiments, the term "low RI" used in conjunction with the first low RI layer or the third layer includes about 1.3 to about 1.7. In one or more embodiments, the term "high RI" used together with the second high RI layer or the third layer includes about 1.6 to about 2.5. In some embodiments, the term "medium RI" used with the third layer includes about 1.55 to about 1.8. In some cases, the ranges of low RI, high RI, and medium RI overlap; however, in most cases, the RI of each layer of the anti-reflective coating 120 has a general correlation: low RI<medium RI<high RI.

As shown in Figure 4, the third layer 130C can be configured as a separate layer independent of the circulation section 130, and instead of the covering layer 131 or in addition to the covering layer 131, it is arranged between one or more circulation sections and the additional coating 140 . As shown in FIG. 5, the third layer can also be configured as a separate layer independent of the circulation section 130, and is provided between the substrate 110 and the plurality of circulation sections 130.

Example materials suitable for the anti-reflective coating 120 include: SiO ₂ , Al ₂ O ₃ , GeO ₂ , SiO, AlOxNy, AlN, SiNx, SiO _x N _y , Si _u Al _v O _x N _y , Ta ₂ O ₅ , Nb _{2 O 5, TiO 2, ZrO} 2, TiN, MgO, MgF 2, BaF 2, CaF 2, SnO 2, HfO 2, Y 2 O 3, MoO 3, DyF 3, YbF 3, YF 3, CeF 3, the polymerization Materials, fluoropolymers, plasma polymerized polymers, silicone polymers, semisiloxanes, polyimides, fluorinated polyimides, polyetherimides, polyether sulfides, polyphenylene sulfides, poly Carbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic polymer, urethane polymer, polymethyl methacrylate, the following other materials suitable for scratch-resistant layers and Other materials known in this field. Some examples of materials suitable for the first low RI layer include SiO ₂ , Al ₂ O ₃ , GeO ₂ , SiO, AlO _x N _y , SiO _x N _y , Si _u Al _v O _x N _y , MgO, MgAl ₂ O ₄ , _{MgF 2, BaF 2, CaF 2} , DyF 3, YbF 3, YF 3 , and CeF _3. The nitrogen content of the material for the first low RI layer can be minimized (for example, Al ₂ O ₃ and MgAl ₂ O ₄ materials). Some examples of materials suitable for the second high RI layer include Si _u Al _v O _x N _y , Ta ₂ O ₅ , Nb ₂ O ₅ , AlN, Si ₃ N ₄ , AlO _x N _y , SiO _x N _y , HfO ₂ , TiO ₂ , ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , MoO ₃ and diamond-like carbon. The oxygen content of the material for the second high RI layer can be minimized, especially SiNx or AlNx materials. The aforementioned materials can be hydrogenated up to about 30% by weight. If a material with a medium refractive index is desired, some embodiments may use AlN and/or SiO _x N _y . The hardness of the second highest RI layer can be specially characterized. In some embodiments, the hardness measured by the Berkovich indenter hardness test may be about 8 GPa or more, about 10 GPa or more, about 12 GPa or more, about 15 GPa or more, about 18 GPa or more. Above or about 20 GPa or above. In some cases, the second high RI layer material can be deposited as a single layer (ie, a part of a non-anti-reflective coating), as measured by reproducible hardness, the thickness of this single layer is about 500 to 2000 nm.

In one or more embodiments, at least one layer of the anti-reflective coating 120 includes a specific optical thickness range. The "optical thickness" used here is determined by n*d, where "n" refers to the RI of the sublayer, and "d" refers to Refers to the physical thickness of the layer. In one or more embodiments, at least one layer of the anti-reflective coating 120 includes an optical thickness of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In some embodiments, each layer of the anti-reflective coating 120 has an optical thickness of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In some cases, the optical thickness of at least one layer of the anti-reflective coating 120 is about 50 nm or more. In some cases, the first low RI layers each have an optical thickness of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In other cases, each of the second high RI layers has an optical thickness of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In still other cases, the third layer each has an optical thickness of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm.

In some embodiments, the thickness of one or more layers of the anti-reflective coating 120 is minimized. In one or more embodiments, the thickness of the high RI layer and/or the medium RI layer is minimized to be less than about 500 nm. In one or more embodiments, the combined thickness of the high RI layer, the medium RI layer, and/or the high RI layer and the medium RI layer composition is less than about 500 nm.

In one or more embodiments, the physical thickness of the anti-reflective coating 120 is about 800 nm or less. The physical thickness of the anti-reflective coating 120 may be from about 10 nm to about 800 nm, from about 50 nm to about 800 nm, from about 100 nm to about 800 nm, from about 150 nm to about 800 nm, from about 200 nm to about 800 nm, from about 10 nm to about 750 nm, from about 10 nm to about 10 nm. 700nm, about 10nm to about 650nm, about 10nm to about 600nm, about 10nm to about 550nm, about 10nm to about 500nm, about 10nm to about 450nm, about 10nm to about 400nm, about 10nm to about 350nm, about 10nm to about 300nm, From about 50 to about 300 and all ranges and subranges therebetween.

In one or more embodiments, the combined physical thickness of the second high RI layer is characterized. For example, in some embodiments, the combined thickness of the second high RI layer may be about 100 nm or more, about 150 nm or more, about 200 nm or more, or about 500 nm or more. The combined thickness is to calculate the thickness combination of individual high RI layers in the anti-reflective coating 120, even if there is an intermediate low RI layer or other layers. In some embodiments, the second highest The combined physical thickness of the RI layer is greater than 30% of the total physical thickness of the anti-reflective coating, and the second high RI layer also includes a high hardness material (such as nitride or oxynitride). For example, the combined physical thickness of the second high RI layer may be about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 75% or more of the total physical thickness of the anti-reflective coating. Or even about 80% or more.

In some embodiments, most of the high refractive index hard materials of the anti-reflective coating can also be made to have low reflectivity, low color and high wear resistance at the same time, which will be further described later.

In some embodiments, when measuring the anti-reflective surface 122 (for example, to remove the reflection from the uncoated back surface of the object (for example, 114 in Figure 1), for example, use index-matched oil on the back surface coupled to the absorber or use other Known method), the average light reflectivity of the anti-reflection coating 120 in the light wavelength range is about 2% or less, 1.5% or less, 0.75% or less, 0.5% or less, 0.25% or less, 0.1% or less Or even 0.05% or less. In some examples, the anti-reflective coating 120 may exhibit this average light reflectance in other wavelength ranges, such as about 450 nm to about 650 nm, about 420 nm to about 680 nm, about 420 nm to about 700 nm, about 420 nm to about 740 nm, about 420 nm. To about 850nm or about 420nm to about 950nm. In some embodiments, the average light transmittance of the anti-reflective surface 122 in the light wavelength range is about 90% or more, 92% or more, 94% or more, 96% or more, or 98% or more. Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (but it can also be measured at an incident illumination angle of 45 degrees or 60 degrees).

As shown in Figure 6, the article 100 includes one or more additional coatings 140 placed on the anti-reflective coating. In one or more embodiments, the additional coating includes an easy-to-clean coating. An example of a suitable easy-to-clean coating is described in U.S. Patent Application No. 13/690,904 filed on November 30, 2012, entitled "PROCESS FOR MAKING OF GLASS ARTICLES WITH OPTICAL AND EASY-TO-CLEAN COATINGS". The entire application is incorporated herein by reference. The thickness of the easy-to-clean coating may be about 5 nm to about 50 nm, and may include known materials such as fluorinated silane. In some embodiments, the thickness of the easy-to-clean coating may be about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 40 nm. About 25nm, about 1nm to about 20nm, about 1nm to about 15nm, about 1nm to about 10nm, about 5nm to about 50nm, about 10nm to about 50nm, about 15nm to about 50nm, about 7nm to about 20nm, about 7nm to about 15nm , About 7nm to about 12nm or about 7nm to about 10nm and all ranges and subranges therebetween.

The additional coating 140 may include a scratch-resistant coating. The scratch-resistant coating may also be included in one of the layers of the anti-reflective coating 120. Exemplary materials for scratch-resistant coatings include inorganic carbides, nitrides, oxides, diamond-like materials, or combinations of the foregoing. Examples of suitable scratch-resistant coating materials include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal oxycarbides, and/or the above-mentioned combinations. Example metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta, and W. Specific examples of materials that can be used for scratch-resistant coatings include Al ₂ O ₃ , AlN, AlO _x N _y , Si ₃ N ₄ , SiO _x N _y , Si _u Al _v O _x N _y , diamond, diamond-like carbon, Si _x C _y , Si _x O _y C _z , ZrO ₂ , TiO _x N _y and the above composition.

In some embodiments, the additional coating 140 includes a combination of an easy-to-clean material and a scratch-resistant material. In one example, the composition includes an easy-to-clean material and diamond-like carbon. The thickness of this additional coating 140 may be about 5 nm to about 20 nm. The components of the additional coating 140 may be provided in different layers. For example, the diamond-like carbon can be configured as a first layer, and the easy-to-clean material can be configured as a second layer on the first layer of diamond-like carbon. The thickness of the first layer and the second layer may be within the above-mentioned additional coating range. For example, the thickness of the first layer of diamond-like carbon may be about 1 nm to about 20 nm or about 4 nm to about 15 nm (more specifically, about 10 nm), and the thickness of the second layer of easy-to-clean material may be about 1 nm to about 10 nm (more specifically, about 10 nm). Specifically, it is about 6 nm). The diamond-like coating may include tetrahedral amorphous carbon (Ta-C), Ta-C:H and/or a-C-H.

The second aspect of the present invention relates to a method of forming the object. In one embodiment, the method includes providing a substrate with a main surface to the coating chamber, forming a vacuum in the coating chamber, forming a durable anti-reflective coating with a thickness of about 1 μm or less on the main surface, and selectively applying an anti-reflective coating on the main surface. An additional coating is formed on the coating, the additional coating includes at least one of an easy-to-clean coating and a scratch-resistant coating, and the substrate is removed from the coating chamber. In one or more embodiments, the anti-reflective coating and the additional coating are formed in the same coating chamber or in different coating chambers without breaking the vacuum.

In one or more embodiments, the method includes loading the substrate on a carrier, which is then used to move the substrate in and out of different coating chambers under load lock conditions to maintain a vacuum when the substrate is moved.

Various deposition methods can be used to form the anti-reflective coating 120 and/or the additional coating 140, such as vacuum deposition techniques, such as chemical vapor deposition (such as plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition, atmospheric pressure). Chemical vapor deposition and plasma enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (such as reactive or non-reactive sputtering or laser stripping), thermal or electron beam evaporation, and/or atomic layer deposition. Liquid-based methods such as spray coating or slit coating can also be used. When vacuum deposition is used, the along-line process can be used to form the anti-reflective coating 120 and/or the additional coating 140 in a single deposition run. In some cases, vacuum deposition is achieved using linear PECVD sources.

In some embodiments, the method includes controlling the thickness of the anti-reflective coating 120 and/or the additional coating 140 to vary the thickness along at least about 80% of the area of the anti-reflective surface 122 or at any point along the area of the substrate. The difference in thickness does not exceed about 4%. In some embodiments, the thickness of the anti-reflective coating 120 and/or the additional coating 140 does not vary by more than about 4% along at least about 95% of the area of the anti-reflective surface 122.

Instance

The different embodiments will be further illustrated with the following examples. It should be noted that the AlO _x N _y and Si _u Al _v O _x N _{y in the} example can be exchanged as the high refractive index material of the model example, and the ordinary skilled person only needs to adjust the process slightly to regenerate the target refractive index dispersion value. And provide layer thickness design.

Example 1

Example 1 is to provide a glass substrate, the nominal composition of the glass substrate is 69 mol% SiO ₂ , 10 mol% Al ₂ O ₃ , 15 mol% Na ₂ O and 5 mol% MgO, and use The plasma-enhanced chemical vapor deposition (PECVD) process is configured with five layers of anti-reflective coating on the glass substrate, as shown in Table 1 and Figure 7.

Depending on the amount of nitrogen in the layer, the refractive index of the second highest RI layer is about 1.6 to about 2.1. The resulting object is transparent and will exhibit wear resistance after 2000 linear wear test cycles.

Figure 8 illustrates the reflection spectrum of Example 1 in the light wavelength range. The reflectivity of Example 1 along a part of the light wavelength range is less than about 0.5%, and the reflectivity of the entire light wavelength range is about 2% or less.

Model instance 2

Model Example 2 is prepared using the same glass substrate as Example 1.

The reflectance simulation of Model Example 2 is shown in Figure 9 (the thickness shown is not accurate, and it is just for illustration). As shown in Figure 9, the reflectance of Model Example 2 in the wavelength range of about 420 nm to about 620 nm is less than about 0.5%, and the reflectance of the entire light wavelength range is less than 1%.

It should be noted that depending on the material selected and the forming process used, Model Example 2 can be modified to include an additional easy-to-clean coating with a thicker or thinner (for example, about 7 nm to about 15 nm) and a refractive index of about 1.2 to about 1.5.

Model instance 3

Model Example 3 is prepared using the same glass substrate as Example 1, and as listed in Table 3, including anti-reflective coating, DLC coating with a thickness of 6nm or 10nm and placed on the anti-reflective coating and DLC coating Easy-to-clean coating on the surface.

The reflectance of Model Example 3 is simulated for different DLC coating thicknesses and is shown in Figure 10 together. As shown in Figure 10, in terms of the thickness of the two DLC coatings, the reflectivity of Model Example 3 in the light wavelength range is less than about 1%. In the embodiment where the DLC coating is about 6 nm, the reflectivity of the entire light wavelength range is even lower (ie, less than about 0.5%). For clarity, the reflectance spectrum of Model Example 3 with a DLC coating of 6 nm thickness is shown in FIG. 11.

Model instance 4-8

Examples 4-8 use modeling to understand the reflection spectrum of an object, and the object includes the durable anti-reflection coating embodiment. In model examples 4-8, Si _u Al _v O _x N _y and SiO ₂ layer and strengthened aluminum silicate glass substrate are used. The nominal composition of the glass substrate is about 58 mol% SiO ₂ and 17 mol% Al ₂ O ₃ , 17 mol% Na ₂ O, 3 mol% MgO, 0.1 mol% SnO, and 6.5 mol% P ₂ O ₅ .

In order to determine the refractive index dispersion curve of the coating material, DC, RF or RF superimposed DC reactive sputtering is used from silicon, aluminum, silicon and aluminum combination or co-sputtering, or magnesium fluoride targets (respectively). At about 50°C, ion-assisted formation of each coating material layer on the silicon wafer. During the deposition of some layers, the wafer was heated up to 200°C and a 3-inch diameter target was used. The reaction gases used include nitrogen, fluorine and oxygen; argon is used as an inert gas. The RF power is supplied to the silicon target at 13.56 MHz, and the DC power is supplied to the Si target, Al target and other targets.

A spectroscopic ellipsometer was used to measure the refractive index (a function of wavelength) of each formation layer and the glass substrate. The measured refractive index is then used to calculate the reflectance spectra of model examples 4-8. For convenience, the model examples use a single refractive index value in each description table, which corresponds to a point selected from the dispersion curve at a wavelength of about 550 nm.

Example 4 includes 6 layers of anti-reflective coating, as shown in Figure 12 (the thickness shown is not precise, it is intended for illustration) and Table 7, the anti-reflective coating includes layers 210, 220, 230, 240, 250, 260 They are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200.

Table 7: Attributes of model instance 4.

According to the Berkovich indenter hardness test, the hardness of the Si _u Al _v O _x N _y layer is greater than that of the SiO ₂ layer. _{The total thickness of the Si u} Al _v O _x N _y layer is 130 nm, which contains about 47% of the overall coating thickness. . The anti-reflective coating is produced by DC/RF sputtering, and the structure of the anti-reflective coating is similar to the anti-reflective coating of Model Example 4. As shown in Example 15, the coatings exhibited abrasion resistance similar to or better than that of bare glass substrates, and greatly improved abrasion resistance compared to conventional oxide-only anti-reflective coatings. The article according to Example 4 exhibited abrasion similar to that of a bare glass substrate (with no anti-reflective coating placed on it).

Calculate the reflectance of the object in Example 4 at different incident angles or angles of illumination ("AOI") on one side of the object. Figure 13 shows the obtained reflectance spectrum. Using a 10-degree observer as the baseline, the reflected color is measured under D65 and F2 light sources, and the angle of incidence or AOI is increased to approximately 60 degrees from 0 degrees off normal, and the values of a* and b* are plotted. . Figure 14 shows the reflection color diagram.

Example 5 includes 9 layers of anti-reflective coating, as shown in Figure 15 (the thickness shown is not precise, and is intended for illustration only). The anti-reflective coating includes layers 310 (third layer), 320, 330, 340, 350 , 360, 370, 380, and 390 are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200. The relative thickness of each layer is listed in Table 8.

In model example 5, according to the Berkovich indenter hardness test, the hardness of the Si _u Al _v O _x N _y layer is greater than that of the SiO ₂ layer, and _{the total thickness of the Si u} Al _v O _x N _y layer is 133 nm, which includes the overall coating About 29% of layer thickness. It is believed that the article according to Example 5 exhibits abrasion similar to that of a bare glass substrate (with no anti-reflective coating placed on it).

Calculate the reflectance of the object of Example 5 under different incident illumination viewing angles or illumination angles ("AOI") on one side of the object. Figure 16 shows the obtained reflectance spectrum. Also take the 10 degree observer as the baseline, and measure under the D65 light source Measure the reflected color, and increase to about 60 degrees regularly with the incident illumination angle or AOI from 0 degrees off the normal line, and plot the a* and b* values. Figure 17 illustrates the reflection color diagram.

Example 6 includes 10 layers of anti-reflective coating, as shown in Figure 18 (the thickness shown in Figure 18 is not precise and is intended for illustration only) and Table 9, the anti-reflective coating includes layers 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200.

The layers 470, 480, and 490 are impedance matching air, and the layers 400, 410, 420, 430, 440, and 450 are impedance matching glass substrates. Therefore, the thickness of the layer 460 can be modified to be about 0 nm to about 500 nm or about 100 nm to about 2000 nm without affecting the optical properties of the anti-reflective coating or the object.

In model example 6, according to the Berkovich indenter hardness test, the hardness of the Si _u Al _v O _x N _y layer is greater than that of the SiO ₂ layer, and _{the total thickness of the Si u} Al _v O _x N _y layer is 578 nm, which includes the overall coating About 76% of layer thickness. DC/RF sputtering is used to manufacture an anti-reflective coating with a structure very similar to Model Example 6. The anti-reflective coating exhibits substantially better abrasion resistance than bare glass substrates, and is greatly improved compared to conventional anti-reflective coatings with only oxides The abrasion resistance.

Calculate the reflectance of the object of Example 6 on one side under different incident illumination viewing angles or illumination angles ("AOI"). Figure 19 shows the obtained reflectance spectrum. Using a 10-degree observer as the baseline, the reflected color is measured under D65 and F2 light sources, and the angle of incidence or AOI is increased to approximately 60 degrees from 0 degrees off normal, and the values of a* and b* are plotted. . Figure 20 illustrates the reflection color diagram.

Example 7 includes 12 layers of anti-reflective coatings, as shown in Figure 21 (the thickness shown in Figure 21 is not precise and is intended for illustration only) and Table 10, the anti-reflective coating includes layers 500, 505, 510, 515, 520, 530, 540, 550, 560, 570, 580, 590 are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200.

The layers 550, 560, 570, 580, and 590 are impedance-matched air, and the layers 500, 505, 510, 515, 520, and 530 are impedance-matched glass substrates. Therefore, the thickness of the layer 540 can be modified to be about 0 nm to about 5000 nm or about 100 nm to about 2500 nm without affecting the optical properties of the anti-reflective coating or the object.

In model example 7, according to the Berkovich indenter hardness test, the hardness of the Si _u Al _v O _x N _y layer is greater than that of the SiO ₂ layer, and _{the total thickness of the Si u} Al _v O _x N _y layer is 774 nm, which includes the overall coating About 78% of the layer thickness. DC/RF sputtering is used to manufacture an anti-reflective coating with a structure very similar to Model Example 7. The anti-reflective coating exhibits substantially better abrasion resistance than the bare glass substrate, and is greatly improved compared to the conventional anti-reflective coating with only oxide The abrasion resistance, as shown in Example 16 below.

Calculate the reflectance of the object of Example 7 on one side under different incident illumination angles or illumination angles ("AOI"). Figure 22 shows the obtained reflectance spectrum. Also take the 10-degree observer as the baseline, in the D65 light source and F2 Measure the reflected color under the light source, and increase it to approximately 60 degrees with the incident illumination angle or AOI from 0 degree deviation from the normal incidence, and plot the a* and b* values. Figure 23 shows the reflection color diagram.

Example 8 includes 14 layers of anti-reflective coating, as shown in Fig. 24 (the thickness shown in Fig. 24 is not precise and is intended for illustration only), and the anti-reflective coating includes layers 600, 605, 610, 615, 620, 625 , 630, 635, 640, 650, 660, 670, 680, 690 are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200. The relative thickness of each layer is listed in Table 11.

According to the Berkovich indenter hardness test, the hardness of the Si _u Al _v O _x N _y layer is greater than that of the SiO ₂ layer. _{The total thickness of the Si u} Al _v O _x N _y layer is 722 nm, which contains about 66% of the overall coating thickness .

Calculate the reflectance of the object of Example 8 under different incident illumination viewing angles or illumination angles ("AOI") on one side of the object. Figure 25 shows the obtained reflectance spectrum. Using a 10-degree observer as the baseline, the reflected color is measured under D65 and F2 light sources, and the angle of incidence or AOI is increased to approximately 60 degrees from 0 degrees off normal, and the values of a* and b* are plotted. . Figure 26 shows the reflection color diagram.

Model example 9, 10A&10B

Model examples 9, 10A, and 10B use the refractive index and dispersion curves of model examples 4-8 and the refractive index and dispersion curves listed in Table 4-5 above to calculate the reflectance spectra of different anti-reflection coating 120 designs.

Model example 9 includes 6 layers of anti-reflective coatings, each layer is arranged on top of each other in sequence and placed on the strengthened aluminum silicate glass substrate 200. The relative thickness of each layer is listed in Table 12.

Calculate the reflectance of the single-sided object of Model Example 9 under different incident illumination viewing angles or illumination angles ("AOI"). Figure 27 shows the obtained reflectance spectrum. Using a 10-degree observer as the baseline, the reflected color is measured under D65 and F2 light sources, and the angle of incidence or AOI is increased to approximately 60 degrees from 0 degrees off normal, and the values of a* and b* are plotted. . Figure 28 shows the reflection color diagram.

Model examples 10A and 10B each include 8 layers of anti-reflective coating. The layers of the coating are sequentially arranged on top of each other and placed on the strengthened aluminum silicate glass substrate 200. The relative thickness of each layer is listed in Table 13.

Calculate the reflectance of one side of the object of Example 10A and Example 10B under different incident illumination viewing angles or illumination angles ("AOI"). Figures 29 and 30 respectively show the obtained reflectance spectra. Also view at 10 degrees The detector is the baseline, and the reflected color is measured under the D65 and F2 light sources, and with the incident illumination angle or AOI from 0 degrees off the normal incidence, it is increased to about 60 degrees regularly, and the a* and b* values are plotted. Figures 31 and 32 show the reflection color diagrams of Examples 10A and 10B, respectively.

Compare the optical properties of model examples 4, 7, 9, 10A, 10B with model comparison example 11. Example 11 includes _{6-layer anti-reflection coating with alternating Nb 2} O ₅ and SiO ₂ layers and a hydrophobic layer placed on the anti-reflection coating Sexual coating. To produce the model comparison example 11, ion-assisted electron beam deposition was used to deposit a single layer of Nb ₂ O _{5 on the} silicon wafer and a single layer of SiO _{2 on the} silicon wafer. A spectroscopic ellipsometer is used to measure the refractive index of the layers with wavelength. The measured refractive index was then used in Model Comparative Example 11. The evaluated optical performance includes the average reflectance in the wavelength range of about 450nm to about 650nm and the color shift when observed under F02 and D65 light sources at an incidence angle of about 0 degrees to about 60 degrees off normal incidence (refer to a* And b* coordinates (-1, -1) and use the formula √((a* _example -(-1)) ² +(b* _example -(-1)) ² )). Table 14 shows the average reflectance and maximum color shift of model examples 4, 7, 9, 10A, 10B and model comparison example 11.

As shown in Table 14, although Model Comparative Example 11 has the smallest average reflectance, it also exhibits the largest color shift. Model Example 4 has comparable reflectivity and significantly reduced color cast. Model examples 7, 9, 10A, and 10B have smaller color shifts, but slightly larger reflectivity.

Examples 12-18

As shown in Table 15, Examples 12-18 include bare aluminum silicate glass substrates (without coating) or aluminum silicate glass substrates with various anti-reflection or hard coatings. The aluminum silicate glass substrate is chemically strengthened, and has a compressive stress of about 700 MPa to about 900 MPa and a compressive stress layer depth value of about 40 μm to about 50 μm. The anti-reflective coating is deposited by reactive DC sputtering, electron beam evaporation, and reactive DC and RF sputtering. The anti-reflective coating includes SiO ₂ , Si _u Al _v O _x N _y , AlO _x N _y and Nb ₂ O ₅ layers. As listed in Table 15, the SiO ₂ layer is formed by ion-assisted DC reactive sputtering at about 200° C. or ion-assisted electron beam deposition. The Nb ₂ O ₅ layer deposition system uses ion-assisted electron beam deposition. The Si _u Al _v O _x N _y layer deposition system uses ion-assisted DC reactive sputtering combined with RF superimposed DC sputtering and heating the substrate to 200°C. The Si _u Al _v O _x N _y layer is made by reactive sputtering in the AJA-Industrial Sputter Deposition Tool. The target materials used to form the Si _u Al _v O _x N _y layer are Si with a diameter of 3" and Al with a diameter of 3". The reactive gases are nitrogen and oxygen, and the "working" (or inert) gas is argon. The power supplied to the Si target is a radio frequency (RF) of 13.56 MHz. The power supplied to the Al target is DC. It should be noted that the AlO _x N _y layer can replace the Si _u Al _v O _x N _y layer, and can be formed by the same or similar layer forming process. The Si _u Al _v O _x N _y and AlO _x N _y layers can be made to have a refractive index of about 1.95 at 550 nm, and the hardness measured by the Berkovich indenter hardness test is greater than 15 GPa.

Table 16 shows the abrasion resistance of Examples 12-13 and Comparative Examples 14-18. This is based on the measured scattered light intensity (CCBTDF, 1/sphericity) and penetration turbidity (using 8mm Aperture). In the absence of abrasion (single surface measurement, minus 4% reflectance from the relative uncoated surface), the average reflectance of the anti-reflective surface is measured.

As shown in Table 16, Examples 12 and 13 are approximately wear-free (or without the Taber test) at 40 degrees to compare the scattered light intensity of Example 18, which indicates better wear resistance. Examples 12 and 13 also show that all samples have the smallest scattered light intensity at 20 degrees after being tested by Taber. The penetration turbidity of Examples 12 and 13 is substantially the same as the penetration turbidity of Comparative Example 18 without abrasion. The average reflectance of Examples 12 and 13 is significantly better than that of Comparative Example 18, and only Comparative Example 14 has a smaller average reflectance.

Figure 33 is a graph of scattered light intensity (CCBTDF, 1/steradian) measured at polar angles along the vertical wear direction in Examples 12-13 and Comparative Examples 15-17 in Table 16 without or after the Taber test. A low scattering intensity value means less severe wear and therefore better wear resistance (and reduced wear visibility for manual inspection).

The AFM roughness was used to evaluate the abrasion resistance of Examples 12-13 and Comparative Examples 14, 17-18 after the Taber test. Table 17 lists the AFM roughness statistics (mean and standard deviation) obtained by scanning the 80×80 micron area of the wear area for 5 times. As shown in Table 17, the roughness of Examples 12 and 13 is much lower than that of Comparative Examples 14 and 18. As shown in Table 17 above, Comparative Example 17 has low roughness, but also has greater reflectivity and light scattering.

Figure 34 is the AFM roughness statistics of Table 22.

Example 19

Example 19 includes 10 layers of anti-reflective coating placed on a strengthened aluminum silicate glass substrate. The nominal composition of the glass substrate is about 58 mol% SiO ₂ , 17 mol% Al ₂ O ₃ , and 17 mol% Na ₂ O, 3 mol% MgO, 0.1 mol% SnO, and 6.5 mol% P ₂ O ₅ . The thickness of each layer is listed in Table 18.

Both the SiO ₂ and Si _u Al _v O _x N _y layers were made by reflective sputtering in a coater manufactured by AJA Industries. The SiO ₂ system uses ion-assisted DC reflective sputtering deposition from the Si target; the Si _u Al _v O _x N _y material uses DC reflective sputtering combined with ion-assisted RF superimposed DC sputtering deposition. The reactive gases are nitrogen and oxygen, and the "working" (or inert) gas is argon.

The amount of high RI material accounted for about 51.5% of the anti-reflective coating, and the amount of low RI material was about 48.5%. The deposition conditions are listed in Table 19. The deposition temperature is 200°C.

Using the obtained dispersion curves of each coating material and the glass substrate, the reflection value of a single side of the object of Example 19 under different incident illumination viewing angles or illumination angles ("AOI") was modeled. Figure 35 shows the resulting model Type reflection spectrum. Using a 10-degree observer as the baseline, the reflected color and penetration color are measured under the D65 light source and F2 light source, and with the incident illumination angle or AOI from 0 degrees off the normal, the regular increments are about 60 degrees. For a* and b *Value mapping. Figure 36 shows the reflection color and transmission color of Example 19. As shown in Figure 36 and Table 21 below, when the incident illumination angle is from 0 degrees to about 60 degrees, the reflection and transmission colors deviating from a*=0 and b*=0 are less than 3. Example 19 was evaluated for the photoreflectivity of different AOIs. The suitable light reflectance from about 0 degrees to about 20 degrees AOI is about 0.4 or less.

Example 20

Example 20 includes 10 layers of anti-reflective coating placed on a reinforced aluminum silicate glass substrate, the nominal composition of the glass substrate is about 58 mol% SiO ₂ , 17 mol% Al ₂ O ₃ , and 17 mol% Na ₂ O, 3 mol% MgO, 0.1 mol% SnO, and 6.5 mol% P ₂ O ₅ . The thickness of each layer is listed in Table 22.

The SiO ₂ and Si _u Al _v O _x N _y layers were made by reflective sputtering in a coater manufactured by Optorum Co., Ltd. The SiO ₂ system uses ion-assisted DC reflective sputtering deposition from the Si target; the Si _u Al _v O _x N _y material uses DC reflective sputtering combined with ion-assisted RF superimposed DC sputtering deposition. The reactive gases are nitrogen and oxygen, and the "working" (or inert) gas is argon. The deposition conditions of the SiO ₂ and Si _u Al _v O _x N _y layers are listed in Table 23. Each layer is formed at a deposition temperature of 200°C, and the deposition time is sufficient to form a physical thickness of each layer.

Table 22: Attributes of Example 20.

In Example 20, the single-sided average reflectance (measured from the anti-reflection surface 122) of the light wavelength range at the incident illumination angles of 0 degrees, 30 degrees, 45 degrees, and 60 degrees were 0.86%, 1.04%, 1.6%, and 3.61%, respectively. In Example 20, the single-sided average transmittance (i.e. measured from the anti-reflection surface 122) at the incident illumination angles of 0 degrees, 30 degrees, 45 degrees and 60 degrees in the light wavelength range was 99.14%, 98.95%, 98.4% and 96.39%, respectively .

Example 20 The total average reflectance (i.e. measured from the anti-reflection surface 122 and the relative main surface 114) at the incident illumination angle of 0 degrees, 30 degrees, 45 degrees and 60 degrees in the light wavelength range is 4.85%, 3.56%, and 2.44%, respectively And 3.77%. In Example 20, the total average transmittance (measured from the anti-reflection surface 122 and the opposite main surface 114) of the light wavelength range at the incident illumination angles of 0 degrees, 30 degrees, 45 degrees, and 60 degrees were 95.15%, 96.44%, and 97.56, respectively. % And 96.23%.

The single surface (i.e., anti-reflection surface 122) and two surfaces (i.e., anti-reflection surface 122 and the main surface 114 of Figure 1) of Example 20 are incident illumination angles or AOI and D65 and F2 from 0 degrees to 60 degrees (or 75 degrees) The reflected and transmitted color coordinates under the light source are listed in Tables 24A-24D. As known in the art, a single surface color coordinate is measured by eliminating the penetration or reflection of the main surface 114. Use the following formula: √((a* ₂ -a* ₁ ) ² +(b* ₂ -b* ₁ ) ² ) to calculate the color shift, where a* ₁ and b* ₁ represent normal incidence (ie AOI= 0) Observe the coordinates of the object, a* ₂ and b* ₂ represent the coordinates of the observation object at different or deviated incident illumination angles (ie AOI=1-60 or 1-75).

Example 21

Example 21 includes 10 layers of anti-reflective coating placed on a strengthened aluminum silicate glass substrate, the nominal composition of the glass substrate is about 58 mol% SiO ₂ , 17 mol% Al ₂ O ₃ , and 17 mol% Na ₂ O, 3 mol% MgO, 0.1 mol% SnO, and 6.5 mol% P ₂ O ₅ . The thickness of each layer is listed in Table 25.

The SiO ₂ and AlO _x N _y layers were made by reflective sputtering in a coater manufactured by Optorum Co., Ltd. SiO ₂ is deposited by ion-assisted DC reflective sputtering from Si target; AlO _x N _{y is} deposited by DC reflective sputtering combined with ion-assisted RF superimposed DC sputtering. The reactive gases are nitrogen and oxygen, and the "working" (or inert) gas is argon. The deposition conditions of the SiO ₂ and AlO _x N _y layers are listed in Table 26. Each layer is formed at a deposition temperature of 200°C, and the deposition time is sufficient to form a physical thickness of each layer.

Using the D65 light source, measure the penetrating color coordinates of the anti-reflective surface of Example 21 and the relatively bare surface of Example 21 with normal incidence, which is shown in Figure 37 and labeled T(D65). Using the F2 light source, only measure the reflected color coordinates of the anti-reflection surface at the incident illumination angle of 20 degrees, 40 degrees, and 60 degrees and the reference illumination angle of 6 degrees. This is also depicted in Figure 37 and marked as R(F2). The measured substrate penetration and reflection color coordinates are plotted in Fig. 37 and are marked as T (glass) and R (glass), respectively. As shown in Fig. 37, the penetration color shift of the object relative to the penetration color coordinate of the substrate is very small (ie, less than about 0.5). In the reflected illumination angle (a*=-0.53, b*=2.08) and incident angle of 20 degrees (a*=-0.9, b*=1.95), 40 degrees (a*=-1.7, b*=0.69) and 60 The reflected color shifts of the relative viewing angle between degrees (a*=-0.44, b*=-1.89) are 0.39, 1.81, and 3.96, respectively.

Figure 38 illustrates the reflectance spectra of Example 21 at the reference illumination angle and incident viewing angle of 20 degrees, 40 degrees, and 60 degrees when only the anti-reflection surface is measured. The average emission and photophobicity of Example 21 are calculated to be 0.54%. Figure 39 shows the measurement of the penetration and reflection spectra of the anti-reflection surface and the opposite bare surface at a reference illumination angle (6 degrees).

When measuring the anti-reflection surface, the measured hardness and Young's modulus of Example 21 were 11.1 GPa and 110 GPa, respectively. The example of Model Comparative Example 11 exhibited a hardness of about 6.8 GPa.

Those who are familiar with this technology will understand that various modifications and changes can be made without departing from the spirit or scope of the present invention.

100‧‧‧Object

110‧‧‧Substrate

120‧‧‧Anti-reflective coating

130‧‧‧Circulation Festival

130A‧‧‧Low RI layer

130B‧‧‧High RI layer

130C‧‧‧Floor

Claims (13)

A durable anti-reflection object, comprising: a substrate having a main surface; and an anti-reflection coating having a thickness of about 0.2 μm to about 1 μm and placed on the main surface, the anti-reflection coating comprising an anti-reflection coating Surface, wherein the anti-reflective coating includes a plurality of layers, the plurality of layers includes at least one low refractive index (RI) layer and at least one high RI layer, the at least one low RI layer is disposed on the main surface of the substrate and A total physical thickness of the high RI layer in contact with the main surface of the substrate is greater than 30% of the total physical thickness of the anti-reflective coating, wherein the main surface of the substrate is disposed on the main surface of the substrate and contacts the substrate. The at least one low RI layer on the surface has an optical thickness ranging from about 15 nm to about 100 nm, where the object exhibits a maximum of about 8 GPa or more as measured along an indentation depth of about 50 nm or more according to the Berkovich indenter hardness test. Hardness, which is only measured on the anti-reflective surface under all human radiation angles ranging from about 0 degrees to about 60 degrees, and the object appears in the CIE L*, a*, b* colorimetric system in terms of reflection. A b* value ranging from about -5 to about 1, and the object exhibits one or both of the following: a single-sided average light transmittance of about 94% or more in a light wavelength range, and a single-sided light The reflectance is about 2% or less in the light wavelength range. The object according to claim 1, wherein the b* value is measured under an F2 light source. The object described in claim 1 or claim 2, wherein the object presents: the anti-reflective surface is measured in accordance with an International Commission on Illumination, and the normal is incident on a (L*, a*, b*) colorimetric system The color shift of a reference point where the penetration color coordinate of an object deviates from a reference point is less than about 2. The reference point includes at least one of a color coordinate (a*=0, b*=0) and a penetration color coordinate of the substrate Measure the anti-reflective surface according to an International Commission on Illumination and Light Sources, and the reflection color coordinate of an object of the (L*, a*, b*) colorimetric system is incident on the normal line. The color shift of a reference point deviates from a reference point. Is less than about 5, the reference point includes at least one of a color coordinate (a*=0, b*=0), a color coordinate (a*=-2, b*=-2), and a reflection color coordinate of the substrate , Where when the reference point is the color coordinate (a*=0, b*=0), the color shift is defined as √((a*_物件) ² +(b*_物件) ² ), where when the reference point When it is the color coordinate (a*=-2, b*=-2), the color shift is defined as √((a*_物件+2) ² +(b*_物件+2) ² ), and when the reference When the points are the color coordinates of the substrate, the color shift is defined as √((a* _object-a * _substrate ) ² +(b* _object- b* _substrate ) ² ). The article according to claim 1 or claim 2, wherein the article exhibits any of the following abrasion resistance, including: when measured by a turbidimeter with an aperture, a turbidity of about 1% or less, wherein the A diameter of the aperture is about 8mm. When measured with an atomic force microscope, an average roughness Ra is about 12nm or less. An imaging sphere is used for scattering measurement and a 2mm aperture at a wavelength of 600nm is used to measure penetration with normal incidence. When the intensity of a scattered light at a polar scattering angle of about 40 degrees or less is about 0.05 or less (unit is 1/steradian), and an imaging sphere is used for scattering measurement and a 2mm aperture is used at a wavelength of 600nm , When the penetration is measured with normal incidence, the intensity of a scattered light at a polar scattering angle of about 20 degrees or less is about 0.1 or less (unit is 1/steradian), where the wear resistance is within 500 After the second cycle of wear, use a Taber test to measure. The article according to claim 1 or claim 2, wherein at least one of the low RI layers and at least one of the high RI layers includes an optical thickness (n*d) of about 2 nm to about 200 nm. The article according to claim 1 or claim 2, wherein the anti-reflective coating comprises a thickness from about 200 nm to about 800 nm. The object according to claim 1 or claim 2, wherein the anti-reflection surface is measured under an F2 light source at all angles of normal incidence to an incident illumination angle of about 20 degrees to about 60 degrees, and the object appears to be smaller than A reflection role deviation of about 5, where the role deviation is _{calculated using a formula √((a* 2} -a* ₁ ) ² +(b* ₂ -b* ₁ ) ² ), a* ₁ and b* ₁ represent Observe the coordinates of the object with normal incidence, and a* ₂ and b* ₂ represent the coordinates of observation of the object with the incident illumination angle. The object described in claim 1 or claim 2 exhibits a reflection spectrum such that a maximum reflectance (R400-max) in a wavelength range of about 400nm to about 480nm is greater than a wavelength of about 500nm to about 600nm A maximum reflectance (R500-max) in the range and a maximum reflectance (R640-max) in a wavelength range from about 640nm to about 710nm, and a maximum reflectance (R640-max) in a wavelength range from about 400nm to about 480nm The minimum reflectance (R400-min) selectivity is less than a minimum reflectance (R500-min) in a wavelength range from about 500nm to about 600nm, and a minimum reflectance in a wavelength range from about 640nm to about 710nm The selectivity (R640-min) is less than R500-min. The article according to claim 1 or claim 2, wherein the substrate includes an amorphous substrate or a crystalline substrate. The article according to claim 9, wherein the amorphous substrate comprises a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass and alkali alumino borosilicate glass , Wherein the glass is selectively chemically strengthened and includes a compressive stress (CS) layer with a surface CS of at least 250 MPa, the CS layer in the chemically strengthened glass from a surface of the chemically strengthened glass Extending to a depth of one layer (DOL), the DOL is at least about 10 μm. The object described in claim 1 or claim 2, wherein each high RI layer contains Si ₃ N ₄ , SiN _x , SiO _x N _y , or Si _u Al _y O _x N _y . The article according to claim 1 or claim 2, wherein the substrate is a glass ceramic substrate. A device comprising a durable anti-reflection object, the durable anti-reflection object being the durable anti-reflection object according to any one of claims 1 to 12.

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